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Sample records for biocatalytic alkene oxidation

  1. Techno-economic analysis of biocatalytic processes for production of alkene epoxides.

    PubMed

    Borole, Abhijeet P; Davison, Brian H

    2007-04-01

    A techno-economic analysis of two different bioprocesses was conducted, one for the conversion of propylene to propylene oxide (PO) and other for conversion of styrene to styrene epoxide (SO). The first process was a lipase-mediated chemo-enzymatic reaction, whereas the second one was a one-step enzymatic process using chloroperoxidase. The PO produced through the chemo-enzymatic process is a racemic product, whereas the latter process (based on chloroperoxidase) produces an enantio-pure product. The former process thus falls under the category of high-volume commodity chemical (PO); whereas the latter is a low-volume, high-value product (SO).A simulation of the process was conducted using the bioprocess engineering software SuperPro Designer v6.0 (Intelligen, Inc., Scotch Plains, NJ) to determine the economic feasibility of the process. The purpose of the exercise was to compare biocatalytic processes with existing chemical processes for production of alkene expoxides. The results show that further improvements are needed in improving biocatalyst stability to make these bioprocesses competitive with chemical processes.

  2. Techno-economic analysis of biocatalytic processes for production of alkene expoxides

    SciTech Connect

    Borole, Abhijeet P

    2007-01-01

    A techno-economic analysis of two different bioprocesses was conducted, one for the conversion of propylene to propylene oxide (PO) and other for conversion of styrene to styrene expoxide (SO). The first process was a lipase-mediated chemo-enzymatic reaction, whereas the second one was a one-step enzymatic process using chloroperoxidase. The PO produced through the chemo-enzymatic process is a racemic product, whereas the latter process (based on chloroperoxidase) produces an enantio-pure product. The former process thus falls under the category of high-volume commodity chemical (PO); whereas the latter is a low-volume, high-value product (SO).A simulation of the process was conducted using the bioprocess engineering software SuperPro Designer v6.0 (Intelligen, Inc., Scotch Plains, NJ) to determine the economic feasibility of the process. The purpose of the exercise was to compare biocatalytic processes with existing chemical processes for production of alkene expoxides. The results show that further improvements are needed in improving biocatalyst stability to make these bioprocesses competitive with chemical processes.

  3. Alkene Cleavage Catalysed by Heme and Nonheme Enzymes: Reaction Mechanisms and Biocatalytic Applications

    PubMed Central

    Mutti, Francesco G.

    2012-01-01

    The oxidative cleavage of alkenes is classically performed by chemical methods, although they display several drawbacks. Ozonolysis requires harsh conditions (−78°C, for a safe process) and reducing reagents in a molar amount, whereas the use of poisonous heavy metals such as Cr, Os, or Ru as catalysts is additionally plagued by low yield and selectivity. Conversely, heme and nonheme enzymes can catalyse the oxidative alkene cleavage at ambient temperature and atmospheric pressure in an aqueous buffer, showing excellent chemo- and regioselectivities in certain cases. This paper focuses on the alkene cleavage catalysed by iron cofactor-dependent enzymes encompassing the reaction mechanisms (in case where it is known) and the application of these enzymes in biocatalysis. PMID:22811656

  4. Biocatalytic Asymmetric Alkene Reduction: Crystal Structure and Characterization of a Double Bond Reductase from Nicotiana tabacum

    PubMed Central

    2013-01-01

    The application of biocatalysis for the asymmetric reduction of activated C=C is a powerful tool for the manufacture of high-value chemical commodities. The biocatalytic potential of “-ene” reductases from the Old Yellow Enzyme (OYE) family of oxidoreductases is well-known; however, the specificity of these enzymes toward mainly small molecule substrates has highlighted the need to discover “-ene” reductases from different enzymatic classes to broaden industrial applicability. Here, we describe the characterization of a flavin-free double bond reductase from Nicotiana tabacum (NtDBR), which belongs to the leukotriene B4 dehydrogenase (LTD) subfamily of the zinc-independent, medium chain dehydrogenase/reductase superfamily of enzymes. Using steady-state kinetics and biotransformation reactions, we have demonstrated the regio- and stereospecificity of NtDBR against a variety of α,β-unsaturated activated alkenes. In addition to catalyzing the reduction of typical LTD substrates and several classical OYE-like substrates, NtDBR also exhibited complementary activity by reducing non-OYE substrates (i.e., reducing the exocyclic C=C double bond of (R)-pulegone) and in some cases showing an opposite stereopreference in comparison with the OYE family member pentaerythritol tetranitrate (PETN) reductase. This serves to augment classical OYE “-ene” reductase activity and, coupled with its aerobic stability, emphasizes the potential industrial value of NtDBR. Furthermore, we also report the X-ray crystal structures of the holo-, binary NADP(H)-bound, and ternary [NADP+ and 4-hydroxy-3-methoxycinnamaldehyde (9a)-bound] NtDBR complexes. These will underpin structure-driven site-saturated mutagenesis studies aimed at enhancing the reactivity, stereochemistry, and specificity of this enzyme. PMID:27547488

  5. Synthesis of trisubstituted alkenes via direct oxidative arene-alkene coupling.

    PubMed

    Jones, Roderick C; Gałęzowski, Michał; O'Shea, Donal F

    2013-08-16

    The use of an inorganic oxidant with an acetic acid/acetonitrile solvent combination has been identified as optimal for direct arene/1,2-disubstituted alkene oxidative couplings, providing an efficient route to trisubstituted alkenes. The acetonitrile cosolvent dramatically accelerates the rate of reaction, and an insoluble inorganic oxidant limits unwanted oxidation of substrates. The scope of this procedure is illustrated with arenes and alkenes containing electron-donating and -withdrawing substituents resulting in a general synthetic strategy to trisubstituted alkenes. In situ ESI-MS analysis of the reaction components has identified the key Pd intermediates in the Fujiwara-Moritani catalytic cycle.

  6. Oxidative Decarboxylation of Short-Chain Fatty Acids to 1-Alkenes.

    PubMed

    Dennig, Alexander; Kuhn, Miriam; Tassoti, Sebastian; Thiessenhusen, Anja; Gilch, Stefan; Bülter, Thomas; Haas, Thomas; Hall, Mélanie; Faber, Kurt

    2015-07-20

    The enzymatic oxidative decarboxylation of linear short-chain fatty acids (C4:0-C9:0) employing the P450 monooxygenase OleT, O2 as the oxidant, and NAD(P)H as the electron donor gave the corresponding terminal C3 to C8  alkenes with product titers of up to 0.93 g L(-1) and TTNs of >2000. Key to this process was the construction of an efficient electron-transfer chain employing putidaredoxin CamAB in combination with NAD(P)H recycling at the expense of glucose, formate, or phosphite. This system allows for the biocatalytic production of industrially important 1-alkenes, such as propene and 1-octene, from renewable resources for the first time.

  7. Engineering of TM1459 from Thermotoga maritima for Increased Oxidative Alkene Cleavage Activity

    PubMed Central

    Fink, Matthias; Trunk, Sarah; Hall, Mélanie; Schwab, Helmut; Steiner, Kerstin

    2016-01-01

    Oxidative cleavage of alkenes is a widely employed process allowing oxyfunctionalization to corresponding carbonyl compounds. Recently, a novel biocatalytic oxidative alkene cleavage activity on styrene derivatives was identified in TM1459 from Thermotoga maritima. In this work we engineered the enzyme by site-saturation mutagenesis of active site amino acids to increase its activity and to broaden its substrate scope. A high-throughput assay for the detection of the ketone products was successfully developed. Several variants with up to twofold improved conversion level of styrene derivatives were successfully identified. Especially, changes in or removal of the C-terminus of TM1459 increased the activity most significantly. These best variants also displayed a slightly enlarged substrate scope. PMID:27713741

  8. Molecular structural characteristics governing biocatalytic oxidation of PAHs with hemoglobin.

    PubMed

    Niu, Junfeng; Yu, Gang

    2004-09-01

    Based on some fundamental quantum chemical descriptors computed by PM3 hamiltonian, two quantitative structure-activity relationship (QSAR) models for biocatalytic oxidation specific activity of unmodified and chemically modified hemoglobin in the oxidation of different polycyclic aromatic hydrocarbons (PAHs) in 15% acetonitrile were developed, respectively, using partial least squares analysis (PLS). The cross-validated Q(cum)(2) values for the two optimal QSAR models are 0.785 and 0.747, respectively, indicating a good predictive ability for biocatalytic oxidation specific activity of PAHs. The main factors affecting specific activity of PAHs are most positive net atomic charges on a hydrogen atom (q(H)(+)), largest negative atomic charge on a carbon atom (q(C)(-)), dipole moment (μ), the energy of the highest occupied molecular orbital (E(HOMO)), and (E(LUMO) - E(HOMO))(2). The biocatalytic oxidation specific activity of PAHs with big q(C)(-) and (E(LUMO) - E(HOMO))(2) values tends to be slow. Increasing q(H)(+), μ, and E(HOMO) values of PAHs leads to increase of specific activity.

  9. Recent biocatalytic oxidation-reduction cascades.

    PubMed

    Schrittwieser, Joerg H; Sattler, Johann; Resch, Verena; Mutti, Francesco G; Kroutil, Wolfgang

    2011-04-01

    The combination of an oxidation and a reduction in a cascade allows performing transformations in a very economic and efficient fashion. The challenge is how to combine an oxidation with a reduction in one pot, either by running the two reactions simultaneously or in a stepwise fashion without isolation of intermediates. The broader availability of various redox enzymes nowadays has triggered the recent investigation of various oxidation-reduction cascades. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Palladium-catalyzed oxidative amination of alkenes: improved catalyst reoxidation enables the use of alkene as the limiting reagent.

    PubMed

    Rogers, Michelle M; Kotov, Vasily; Chatwichien, Jaruwan; Stahl, Shannon S

    2007-10-11

    Palladium-catalyzed methods for intermolecular aerobic oxidative amination of alkenes have been identified that are compatible with the use of alkene as the limiting reagent. These procedures, which enhance the utility of this reaction with alkenes that are not commercially available, are demonstrated with substrates bearing dialkyl ether, carboxyester, epoxide, and silyl ether groups.

  11. Biocatalytic and biomimetic oxidations with vanadium.

    PubMed

    van de Velde, F; Arends, I W; Sheldon, R A

    2000-05-30

    Approaches to the rational design of vanadium-based semi-synthetic enzymes and biomimetic models as catalysts for enantioselective oxidations are reviewed. Incorporation of vanadate ion into the active site of phytase (E.C. 3.1.3.8), which in vivo mediates the hydrolysis of phosphate esters, afforded a semi-synthetic peroxidase. It catalyzed the enantioselective oxidation of prochiral sulfides with H2O2 affording the S-sulfoxide, e.g. in 66% ee at quantitative conversion of thioanisole. Under the reaction conditions the semi-synthetic vanadium peroxidase was stable for more than 3 days with only a slight decrease in turnover frequency. Amongst the transition-metal oxoanions that are known to be potent inhibitors of phosphatases, only vanadate resulted in a semi-synthetic peroxidase when incorporated into phytase. In a biomimetic approach, vanadium complexes of chiral Schiff base complexes were encapsulated in the super cages of a hydrophobic zeolite Y. Unfortunately, these ship-in-a-bottle complexes afforded only racemic sulfoxide in the catalytic oxidation of thioanisole with H2O2.

  12. Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes.

    PubMed

    Xiong, Peng; Xu, Fan; Qian, Xiang-Yang; Yohannes, Yared; Song, Jinshuai; Lu, Xin; Xu, Hai-Chao

    2016-03-18

    A copper-catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker-type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β-hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess-Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di- and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical-organometallic mechanism involving an amidyl radical cyclization to form the key C-N bond. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Chemical modification of hemoglobin improves biocatalytic oxidation of PAHs.

    PubMed

    Torres, E; Vazquez-Duhalt, R

    2000-07-14

    Chemical modifications on human hemoglobin were performed with the aim to change both surface and active-site hydrophobicities. The modifications included covalent coupling of poly(ethylene)glycol (5000 MW) on free amino groups and the methyl esterification of free carboxylic groups. The modified hemoglobin was assayed for the oxidation of 11 polycyclic aromatic hydrocarbons (PAHs) and 2 organosulfur aromatic compounds. Acenaphthene, anthracene, azulene, benzo(a)pyrene, fluoranthene, fluorene, phenanthrene, and pyrene were transformed to their respective quinones, while for chrysene and biphenyl no biocatalytic reaction could be detected. Dibenzothiophene and thianthrene were oxidized to form sulfoxides. The doubly modified hemoglobin, PEG-Met-hemoglobin, showed up to 10 times higher activity than the unmodified protein. The kinetic constants show that the PEG-Met-hemoglobin has a significantly higher catalytic efficiency. The equilibrium substrate binding constants for unmodified and PEG-Met-modified hemoglobis and hemoglobin show that this catalytic enhancement could be attributed to the affinity increase for hydrophobic substrates in the modified protein. Copyright 2000 Academic Press.

  14. Metal-catalyzed oxidation of 2-alkenals generates genotoxic 4-oxo-2-alkenals during lipid peroxidation.

    PubMed

    Nuka, Erika; Tomono, Susumu; Ishisaka, Akari; Kato, Yoji; Miyoshi, Noriyuki; Kawai, Yoshichika

    2016-10-01

    Lipid peroxidation products react with cellular molecules, such as DNA bases, to form covalent adducts, which are associated with aging and disease processes. Since lipid peroxidation is a complex process and occurs in multiple stages, there might be yet unknown reaction pathways. Here, we analyzed comprehensively 2'-deoxyguanosine (dG) adducts with oxidized arachidonic acid using liquid chromatography-tandem mass spectrometry and found the formation of 7-(2-oxo-hexyl)-etheno-dG as one of the major unidentified adducts. The formation of this adduct was reproduced in the reaction of dG with 2-octenal and predominantly with 4-oxo-2-octenal (OOE). We also found that other 2-alkenals (with five or more carbons) generate corresponding 4-oxo-2-alkenal-type adducts. Importantly, it was found that transition metals enhanced the oxidation of C4-position of 2-octenal, leading to the formation of OOE-dG adduct. These findings demonstrated a new pathway for the formation of 4-oxo-2-alkenals during lipid peroxidation and might provide a mechanism for metal-catalyzed genotoxicity.

  15. Oxidations of alkenes and lignin model compounds in aqueous dispersions

    SciTech Connect

    Zhu, Weiming.

    1991-01-01

    The objective was to develop methods to oxidize water-immiscible alkenes and lignin model compounds with polymer colloid supported transition metal catalysts. The oxidations of organic compounds were carried out in aqueous phase with several water-soluble oxidants and dioxygen. Cationic polymer latexes were prepared by the emulsion copolymerization of vinylbenzyl chloride, divinylbenzene, and vinyl octadecyl ether, or styrene, or n-decyl methacrylate, and the subsequent quaternization of copolymers with trimethylamine. The latex particles were 44 nm to 71 nm in diameter. The latex bound Mn porphyrin catalysts were formed with MnTSPP [TSPP = meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphyrin], which catalyzed the oxidation of cyclohexene, cycloocetene, allylbenzene, and 1-octene by sodium hypochlorite (NaOCl) and potassium peroxymonosulfate (KHSO[sub 5]). The latex bound porphyrin catalysts showed higher activity than MnTSPP in solution. Oxidations of 3,4-dimethoxybenzyl alcohol (DMBA), 4-hydroxy-3-methoxytoluene (HMT), and 3,4-dimethoxytoluene (DMT) were performed with either dioxygen or hydrogen peroxide and CoPcTS (PcTS = tetrasulfonatophthalocyanine), FePcTS, CuPcTS, NiPcTS, FeTCPP [TCPP = meso-tetrakis(4-carboxyphenyl)porphyrin], and MnTSPP. CoPcTS catalyzed the autoxidation of DMBA and HMT at 70-85[degrees]C and pH [ge] 8. All catalysts were active for the oxidation of DMBA, HMT, and DMT with H[sub 2]O[sub 2]. Aqueous solutions of KHSO[sub 5] oxidized water-immiscible alkenes at room temperature in the absence of organic solvent. The acidic pH [le] 1.7 solutions of commercial 2KHSO[sub 5][center dot]K[sub 2]SO[sub 4] in water produced diols from all reactive alkenes except cyclooctene. Adjustment of initial pH to [ge]6.7 with NaHCO[sub 3] enabled selective epoxidations.

  16. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Walavalkar, M.; Sharma, A.; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, P. D.; Bajaj, P. N.

    2013-03-01

    In view of the importance of the oxidation pathways of alkenes in the troposphere, and the significance of Cl atom as an oxidant in marine boundary layer (MBL) and polluted industrial atmosphere, the reactions of four 1-alkenes (C6-C9) with Cl atoms are investigated. The rate coefficients at 298 K are measured to be (4.0 ± 0.5), (4.4 ± 0.7), (5.5 ± 0.9) and (5.9 ± 1.7) × 10-10 cm3 molecule-1 s-1 for 1-hexene, 1-heptene, 1-octene and 1-nonene, respectively. The quoted errors include the experimental 2σ, along with the error in the reference rate coefficients. From the systematic increase in the rate coefficients with the number of carbon atoms, an approximate value for the average rate coefficient for hydrogen abstraction per CH2 group in alkenes is estimated to be (4.9 ± 0.3) × 10-11 cm3 molecule-1 s-1. Based on these rate coefficients, the contribution of Cl atom reactions towards the degradation of these molecules is found to be comparable to that of OH radical reactions, under MBL conditions. The products identified in gas phase indicate that Cl atom addition occurs mainly at the terminal carbon, leading to the formation of 1-chloro-2-ketones and 1-chloro-2-ols. The major gas phase products from the alkenyl radicals (formed by H atom abstraction) are different positional isomers of long chain enols and enones. A preference for dissociation leading to an allyl radical, resulting in aldehydes, lower by three carbon atoms, is indicated. The observed relative yields suggest that in general, the increased contribution of the reactions of Cl atoms towards degradation of 1-alkenes in NOx free air does not result in an increase in the generation of small aldehydes (carbon number < 4), including chloroethanal, as compared to that in the reaction of 1-butene.

  17. AN EFFICIENT AND ECOFRIENDLY OXIDATION OF ALKENES USING IRON NITRATE AND MOLECULAR OXYGEN

    EPA Science Inventory

    An environmentally friendly solventless oxidation of alkenes is accomplished efficiently using relatively benign iron nitrate as catalyst in the pressence of molecular oxygen under pressurized conditions.

  18. Photocatalytic oxidation of alkenes and alcohols in water by a manganese(v) nitrido complex.

    PubMed

    Chen, Gui; Chen, Lingjing; Ma, Li; Kwong, Hoi-Ki; Lau, Tai-Chu

    2016-07-28

    Mn(v) nitrido complex [Mn(N)(CN)4](2-) is an efficient catalyst for visible-light induced oxidation of alkenes and alcohols in water using [Ru(bpy)3](2+) as a photosensitizer and [Co(NH3)5Cl](2+) as a sacrificial oxidant. Alkenes are oxidized to epoxides and alcohols to carbonyl compounds.

  19. Intermolecular Palladium-Catalyzed Oxidative Fluorocarbonylation of Unactivated Alkenes: Efficient Access to β-Fluorocarboxylic Esters.

    PubMed

    Qi, Xiaoxu; Yu, Feng; Chen, Pinhong; Liu, Guosheng

    2017-10-02

    A novel palladium-catalyzed intermolecular oxidative fluorocarbonylation of alkenes has been developed, in which employment of a cooperative process with electrophilic ArIF2 -meidated alkenes activation and palladium-catalyzed carbonylation is crucial for the successful catalytic transformation. The current transformation presents the first convenient method to generate β-fluorinated carboxylic acid derivatives under mild reaction conditions from simple alkenes with excellent regioselectivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Gold-catalyzed three-component coupling: oxidative oxyarylation of alkenes.

    PubMed

    Melhado, Asa D; Brenzovich, William E; Lackner, Aaron D; Toste, F Dean

    2010-07-07

    The three-component coupling of terminal alkenes with arylboronic acids and oxygen nucleophiles is described. The reaction employs a binuclear gold(I) bromide as a catalyst and Selectfluor reagent as the stoichiometric oxidant. Alcohols, carboxylic acids, and water can be employed as oxygen nucleophiles, thus providing an efficient entry into beta-aryl ethers, esters, and alcohols from alkenes.

  1. A mild oxidative aryl radical addition into alkenes by aerobic oxidation of arylhydrazines.

    PubMed

    Taniguchi, Tsuyoshi; Zaimoku, Hisaaki; Ishibashi, Hiroyuki

    2011-04-04

    A mild and practical oxyarylation of alkenes by oxidative radical addition has been developed by using aerobic oxidation of hydrazine compounds. The use of a catalytic amount of potassium ferrocyanide trihydrate (K(4)[Fe(CN)(6)]⋅3H(2)O) and water accelerated this radical reaction to give peroxides or alcohols from simple alkenes in good yields. The environmentally friendly and economical radical reactions were achieved at room temperature in the presence of iron catalyst, oxygen gas, and water. A method involving aniline as a radical precursor is also described.

  2. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    NASA Astrophysics Data System (ADS)

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.

    2017-07-01

    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  3. Biocatalytic oxidation by chloroperoxidase from Caldariomyces fumago in polymersome nanoreactors.

    PubMed

    de Hoog, H M; Nallani, M; Cornelissen, J J L M; Rowan, A E; Nolte, R J M; Arends, I W C E

    2009-11-21

    The encapsulation of chloroperoxidase from Caldariomyces fumago (CPO) in block copolymer polymersomes is reported. Fluorescence and electron microscopy show that when the encapsulating conditions favour self-assembly of the block copolymer, the enzyme is incorporated with concentrations that are 50 times higher than the enzyme concentration before encapsulation. The oxidation of two substrates by the encapsulated enzyme was studied: i) pyrogallol, a common substrate used to assay CPO enzymatic activity and ii) thioanisole, of which the product, (R)-methyl phenyl sulfoxide, is an important pharmaceutical intermediate. The CPO-loaded polymersomes showed distinct reactivity towards these substrates. While the oxidation of pyrogallol was limited by diffusion of the substrate into the polymersome, the rate-limiting step for the oxidation of thioansiole was the turnover by the enzyme.

  4. Photocatalytic Dehydrogenative Cross-Coupling of Alkenes with Alcohols or Azoles without External Oxidant.

    PubMed

    Yi, Hong; Niu, Linbin; Song, Chunlan; Li, Yiying; Dou, Bowen; Singh, Atul K; Lei, Aiwen

    2017-01-19

    Direct cross-coupling between alkenes/R-H or alkenes/RXH is a dream reaction, especially without external oxidants. Inputting energy by photocatalysis and employing a cobalt catalyst as a two-electron acceptor, a direct C-H/X-H cross-coupling with H2 evolution has been achieved for C-O and C-N bond formation. A new radical alkenylation using alkene as the redox compound is presented. A wide range of aliphatic alcohols-even long chain alcohols-are tolerated well in this system, providing a new route to multi-substituted enol ether derivatives using simple alkenes. Additionally, this protocol can also be used for N-vinylazole synthesis. Mechanistic insights reveal that the cobalt catalyst oxidizes the photocatalyst to revive the photocatalytic cycle.

  5. Biocatalytic process optimization based on mechanistic modeling of cholic acid oxidation with cofactor regeneration.

    PubMed

    Braun, Michael; Link, Hannes; Liu, Luo; Schmid, Rolf D; Weuster-Botz, Dirk

    2011-06-01

    Reduction and oxidation of steroids in the human gut are catalyzed by hydroxysteroid dehydrogenases of microorganisms. For the production of 12-ketochenodeoxycholic acid (12-Keto-CDCA) from cholic acid the biocatalytic application of the 12α-hydroxysteroid dehydrogenase of Clostridium group P, strain C 48-50 (HSDH) is an alternative to chemical synthesis. However, due to the intensive costs the necessary cofactor (NADP(+) ) has to be regenerated. The alcohol dehydrogenase of Thermoanaerobacter ethanolicus (ADH-TE) was applied to catalyze the reduction of acetone while regenerating NADP(+) . A mechanistic kinetic model was developed for the process development of cholic acid oxidation using HSDH and ADH-TE. The process model was derived by identifying the parameters for both enzymatic models separately using progress curve measurements of batch processes over a broad range of concentrations and considering the underlying ordered bi-bi mechanism. Both independently derived kinetic models were coupled via mass balances to predict the production of 12-Keto-CDCA with HSDH and integrated cofactor regeneration with ADH-TE and acetone as co-substrate. The prediction of the derived model was suitable to describe the dynamics of the preparative 12-Keto-CDCA batch production with different initial reactant and enzyme concentrations. These datasets were used again for parameter identification. This led to a combined model which excellently described the reaction dynamics of biocatalytic batch processes over broad concentration ranges. Based on the identified process model batch process optimization was successfully performed in silico to minimize enzyme costs. By using 0.1 mM NADP(+) the HSDH concentration can be reduced to 3-4 µM and the ADH concentration to 0.4-0.6 µM to reach the maximal possible conversion of 100 mM cholic acid within 48 h. In conclusion, the identified mechanistic model offers a powerful tool for a cost-efficient process design. Copyright © 2010 Wiley

  6. Copper-mediated stereospecific C-H oxidative sulfenylation of terminal alkenes with disulfides.

    PubMed

    Tu, Hai-Yong; Hu, Bo-Lun; Deng, Chen-Liang; Zhang, Xing-Guo

    2015-11-04

    A copper and iodine-mediated C-H oxidative sulfenylation of olefins with diaryl disulfides has been developed for the stereospecific synthesis of vinyl thioether. With the combination of Cu(OTf)2 and I2, a variety of terminal alkenes underwent oxidative coupling reaction with various diaryl disulfides successfully to afford the corresponding E-vinyl sulfides in moderate to good yields.

  7. Amidoselenation and Amidotelluration of Alkenes using Oxygen as Terminal Oxidant.

    PubMed

    Sun, Kai; Wang, Xin; Zhang, Chong; Zhang, Saifei; Chen, Yao; Jiao, Hezhen; Du, Weimin

    2017-03-16

    A protocol has been established for oxygen-mediated amidoselenation and amidotelluration of alkenes under mild conditions. This method provides a simple route to a series of structurally diverse β-amido selenides and β-amido tellurides in moderate to high yields. The wide substrate scope, good functional group tolerance, ease of large-scale preparation and potential for product derivatization make this reaction attractive for the synthesis of nitrogen-, selenium- and tellurium-containing molecules.

  8. Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

    NASA Astrophysics Data System (ADS)

    Liu, Yan-Yun; Yang, Xu-Heng; Song, Ren-Jie; Luo, Shenglian; Li, Jin-Heng

    2017-04-01

    Difunctionalization of alkenes has become a powerful tool for quickly increasing molecular complexity in synthesis. Despite significant progress in the area of alkene difunctionalization involving the incorporation of a nitrogen atom across the C-C double bonds, approaches for the direct 1,2-carboamination of alkenes to produce linear N-containing molecules are scarce and remain a formidable challenge. Here we describe a radical-mediated oxidative intermolecular 1,2-alkylamination of alkenes with alkyl nitriles and amines involving C(sp3)-H oxidative functionalization catalysed by a combination of Ag2CO3 with iron Lewis acids. This three-component alkene 1,2-alkylamination method is initiated by the C(sp3)-H oxidative radical functionalization, which enables one-step formation of two new chemical bonds, a C-C bond and a C-N bond, to selectively produce γ-amino alkyl nitriles.

  9. Pd(Quinox)-Catalyzed Allylic Relay Suzuki Reactions of Secondary Homostyrenyl Tosylates via Alkene-Assisted Oxidative Addition.

    PubMed

    Stokes, Benjamin J; Bischoff, Amanda J; Sigman, Matthew S

    2014-06-01

    Pd-catalyzed allylic relay Suzuki cross-coupling reactions of secondary alkyl tosylates, featuring a sterically-hindered oxidative addition and precise control of β-hydride elimination, are reported. The identification of a linear free energy relationship between the relative rates of substrate consumption and the electronic nature of the substrate alkene suggests that the oxidative addition requires direct alkene involvement. A study of the effect of chain length on the reaction outcome supports a chelation-controlled oxidative addition.

  10. Light-driven biocatalytic oxidation and reduction reactions: scope and limitations.

    PubMed

    Taglieber, Andreas; Schulz, Frank; Hollmann, Frank; Rusek, Monika; Reetz, Manfred T

    2008-03-03

    The quest for practical regeneration concepts for nicotinamide-dependent oxidoreductases continues. Recently we proposed the use of visible light to promote the direct reductive regeneration of a flavin-dependent monooxygenase. With this enzyme (PAMO-P3) light-driven enantioselective Baeyer-Villiger oxidations were performed. In spite of the significant reduction in the complexity achieved, catalytic performance of the novel approach did not meet the requirements for an efficient biocatalytic oxygenation system. Driven by this ultimate goal, we further investigated the limiting factors of our particular system. We discovered that oxidative uncoupling of the flavin-regeneration reaction from enzymatic O2-activation accounts for the futile consumption of approximately 95% of the reducing equivalents provided by the sacrificial electron donor, EDTA. Furthermore, it was found that the apparent turnover frequency (TOF) for PAMO-P3 in the present setup is approximately two orders of magnitude lower than in conventional setups that use NADPH as reductant. This finding was traced to sluggish electron transfer kinetics that arose from an impeded interaction between PAMO-P3-bound FAD and the reducing catalyst. The limiting factors and potential approaches for their circumvention are discussed. Furthermore, we broadened the light-driven regeneration approach to the class of flavin-dependent reductases. By using the Old Yellow Enzyme homologue YqjM as a model system, a significantly higher catalytic turnover for the enzyme catalyst was achieved, which we assign to a higher accessibility of the prosthetic group as well as to the absence of oxidative uncoupling.

  11. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    PubMed Central

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-01-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal. PMID:27687877

  12. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    NASA Astrophysics Data System (ADS)

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-09-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

  13. Epoxidation of alkenes and oxidation of alcohols with hydrogen peroxide catalyzed by a manganese(V) nitrido complex.

    PubMed

    Kwong, Hoi-Ki; Lo, Po-Kam; Lau, Kai-Chung; Lau, Tai-Chu

    2011-04-14

    The manganese(V) nitrido complex (PPh(4))(2)[Mn(N)(CN)(4)] is an active catalyst for alkene epoxidation and alcohol oxidation using H(2)O(2) as an oxidant. The catalytic oxidation is greatly enhanced by the addition of just one equivalent of acetic acid. The oxidation of ethene by this system has been studied computationally by the DFT method.

  14. Branched zinc oxide nanorods arrays modified paper electrode for electrochemical immunosensing by combining biocatalytic precipitation reaction and competitive immunoassay mode.

    PubMed

    Sun, Guoqiang; Yang, Hongmei; Zhang, Yan; Yu, Jinghua; Ge, Shenguang; Yan, Mei; Song, Xianrang

    2015-12-15

    Branched zinc oxide nanorods (BZR) arrays, an array with high charge carries collection efficiency and specific surface area, are grown on the reduced graphene oxide-paper working electrode for the first time to construct a paper-based electrochemical (EC) immunosensor. Typically, the BZR are fabricated via a simple hydrothermal process, which can provide abundant sites for antibodies loading. By combining the large surface area of porous zinc oxide (PZS) and good biocompatibility of gold nanoparticles (AuNPs), PZS-AuNPs (PZS@Au) nanocomposites are designed to label horseradish peroxide (HRP) and antigens. After a competitive reaction between antigens and PZS@Au nanocomposites labeled antigens, the signal labels are introduced into the immunosensor, in which, HRP participate in biocatalytic precipitation process. The produced precipitate reduces the electrode surface area and hinders the electron transfer. With the increase of concentration of antigens, the signal labels introduced into the sensor decrease, thus, a signal-on immunoassay for α-fetoprotein detection is constructed. The proposed paper-based EC immunosensor combines enzymatic biocatalytic precipitation reaction and competitive immunoassay mode for the first time, and possesses a wide linear range from 0.2 pg mL(-1) to 500 ng mL(-1) with a detection limit of 0.08 pg mL(-1). In addition, the proposed method is simple, sensitive and specific and can be a promising platform for other protein detection. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide.

    PubMed

    Che, Chi-Ming; Yip, Wing-Ping; Yu, Wing-Yiu

    2006-09-18

    A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me3tacn)(CF3CO2)2Ru(III)(OH2)]CF3CO2 (1; Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80% yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol %. On the one-mole scale, the oxidation of cyclohexene, cyclooctene, and 1-octanol with 1 mol % of 1 produced adipic acid (124 g, 85% yield), suberic acid (158 g, 91% yield), and 1-octanoic acid (129 g, 90% yield), respectively. The oxidative C=C bond-cleavage reaction proceeded through the formation of cis- and trans-diol intermediates, which were further oxidized to carboxylic acids via C-C bond cleavage.

  16. Palladium/Copper-Cocatalyzed Oxidative Amidobrominations of Alkenes.

    PubMed

    Chen, Xiao Yun; Bohmann, Rebekka Anna; Wang, Long; Dong, Shunxi; Räuber, Christoph; Bolm, Carsten

    2015-07-13

    In the presence of LiBr, a palladium/copper combination catalyzes dehydrogenative amidobrominations of acrylates with NH-sulfoximines, leading to N-vinylated products by dual NH/CH coupling, followed by oxidative enamide bromination. Mechanistically, the domino process is proposed to involve palladium(II) species as key intermediates. First synthetic applications of the products have been demonstrated.

  17. Cloud condensation nucleation activity of secondary organic aerosols formed from the oxidation of alkenes and diiodomethane

    NASA Astrophysics Data System (ADS)

    Petters, M. D.; Faulhaber, A.; Prenni, A. J.; Carrico, C. M.; Sullivan, R. C.; Demott, P. J.; Kreidenweis, S. M.; Ziemann, P. J.

    2009-12-01

    Recent measurements have shown that marine aerosol contains a significant fraction of organic compounds. The sources for these compounds are not yet completely understood, but are thought to be a mix of primary emissions and secondary organic aerosol (SOA) formation. Reactive alkenes with low carbon numbers (C5 and C6) and halogenated hydrocarbons emitted from phytoplankton are commonly suggested precursors. These compounds can contribute to new particle formation events and can lead to subsequent growth into the accumulation mode size range. We conducted measurements of the cloud condensation nuclei (CCN) and ice nuclei activity of SOA that was formed from the oxidation of linear, branched, and cyclic alkenes, as well as from diiodomethane. Aerosol forming reactions were carried out in a PTFE environmental chamber, involving oxidation of the precursors mostly with O3 and, for a select number of precursors, oxidation with OH in the absence of NOx. We also performed experiments on single component aerosols generated from the atomization of aqueous solutions, targeting polyalcohols commonly associated with isoprene oxidation products. Ice nucleation experiments were performed only for the O3 reactions and ice nuclei were not observed in detectable quantities for this subset of systems. From our experiments we found that CCN activity generally decreases with the precursor carbon number. When expressed as hygroscopicity parameter (kappa), CCN activity ranged from kappa ~ 0.15 to kappa 0, spanning the range from moderately CCN active to CCN inactive at atmospherically relevant sizes and supersaturations, respectively.

  18. Metabolic alkene labeling and in vitro detection of histone acylation via the aqueous oxidative Heck reaction.

    PubMed

    Ourailidou, Maria E; Dockerty, Paul; Witte, Martin; Poelarends, Gerrit J; Dekker, Frank J

    2015-03-28

    The detection of protein lysine acylations remains a challenge due to lack of specific antibodies for acylations with various chain lengths. This problem can be addressed by metabolic labeling techniques using carboxylates with reactive functionalities. Subsequent chemoselective reactions with a complementary moiety connected to a detection tag enable the visualization and quantification of the protein lysine acylome. In this study, we present EDTA-Pd(II) as a novel catalyst for the oxidative Heck reaction on protein-bound alkenes, which allows employment of fully aqueous reaction conditions. We used this reaction to monitor histone lysine acylation in vitro after metabolic incorporation of olefinic carboxylates as chemical reporters.

  19. Mechanistic Studies of Wacker-Type Intramolecular Aerobic Oxidative Amination of Alkenes Catalyzed by Pd(OAc)2/Pyridine

    PubMed Central

    Ye, Xuan; Liu, Guosheng; Popp, Brian V.; Stahl, Shannon S.

    2011-01-01

    Wacker-type oxidative cyclization reactions have been the subject of extensive research for several decades, but few systematic mechanistic studies of these reactions have been reported. The present study features experimental and DFT computational studies of Pd(OAc)2/pyridine-catalyzed intramolecular aerobic oxidative amination of alkenes. The data support a stepwise catalytic mechanism that consists of (1) steady-state formation of a PdII-amidate-alkene chelate with release of one equivalent of pyridine and AcOH from the catalyst center, (2) alkene insertion into a Pd–N bond, (3) reversible β-hydride elimination, (4) irreversible reductive elimination of AcOH, and (5) aerobic oxidation of palladium(0) to regenerate the active trans-Pd(OAc)2(py)2 catalyst. Evidence is obtained for two energetically viable pathways for the key C–N bond-forming step, featuring a pyridine-ligated and a pyridine-dissociated PdII species. Analysis of natural charges and bond lengths of the alkene-insertion transition state suggest that this reaction is best described as an intramolecular nucleophilic attack of the amidate ligand on the coordinated alkene. PMID:21250706

  20. Enantioselective Oxidation of Alkenes with Potassium Permanganate Catalyzed by Chiral Dicationic Bisguanidinium.

    PubMed

    Wang, Chao; Zong, Lili; Tan, Choon-Hong

    2015-08-26

    Chiral anion-controlled ion-pairing catalysis was demonstrated to be a wide-ranging strategy that can utilize a variety of cationic metal species. In a similar manner, we envision a complementary strategy using chiral cation in partnership with inorganic anionic metal salts. Herein, we report a chiral dicationic bisguanidinium-catalyzed asymmetric oxidation reaction of alkenes with potassium permanganate. Chiral induction is attributed to ion-pairing interaction between chiral cation and enolate anion. The success of the current permanganate oxidation reaction together with mechanistic insights should provide inspiration for expansion to other anionic metal salts and would open up new paradigms for asymmetric transition metal catalysis, phase-transfer catalysis, and ion-pairing catalysis.

  1. Formation of highly oxidized multifunctional compounds: Autoxidation of peroxy radicals formed in the oxidation of alkenes

    NASA Astrophysics Data System (ADS)

    Mentel, Thomas; Ehn, Mikael; Thornton, Joel; Kleist, Einhard; Pullinen, Iida; Springer, Monika; Wahner, Andreas; Wildt, Jürgen

    2015-04-01

    Recent studies show that peroxy radicals are key intermediates in particle formation. Permutation reactions involving highly oxidized peroxy radicals form stable products with extremely low volatility (ELVOC). We suggest that ELVOC are the postulated organic compounds that explain growth of small particles (Ehn et al., Nature, 2014). To elucidate the pathways of ELVOC formation, experiments were performed in the Juelich Plant Atmosphere Chamber. We applied High Resolution Nitrate-Chemical Ionization Mass Spectrometry for detection of ELVOC including highly oxidized peroxy radicals. ELVOC were produced by ozonolysis of a-pinene and other cyclic alkenes (Rissanen et al., JACS, 2014, Mentel et al., ACPD, 2015), as well as by reactions of the target compounds with OH. ELVOC with C10 skeletons carry a large number of oxygens, still containing 14 or 16 H-atoms. ELVOC-dimers with twice the number of C-atoms of the reactant were also observed. The formation of ELVOC can be explained by fast intramolecular H-shifts in combination with classical peroxy radical termination reactions, leading to ketones, alcohols, and hydroperoxides (including peroxy acids). The subsequent H-shifts enable the formation of an increasing number of hydroperoxide groups under reproduction of a peroxy radical (containing now two more oxygens). Addition of NOX to the system increases the concentrations of nitrates at the expense of the corresponding peroxy radicals, confirming their identification as peroxy radicals. Furthermore, the concentrations of ELVOC dimers decrease strongly with increasing NOX suggesting that they are indeed formed by peroxy-peroxy permutation reactions. ELVOC are involved in new particle formation, and can explain the major fraction of the early growth observed in field studies. ELVOC dimers are very likely key in new particle formation as their formation is strongly suppressed with increasing NOX in accordance with the observed NOX dependence of new particle formation (Ehn

  2. Electron ionization mass spectrometry fragmentation pathways of trimethylsilyl derivatives of isomeric allylic alcohols derived from HBI alkene oxidation.

    PubMed

    Rontani, Jean-François; Belt, Simon T; Brown, Thomas A; Aubert, Claude

    2014-09-15

    C25 tri-unsaturated highly branched isoprenoid (HBI) alkenes are produced by a number of marine diatoms around the world yet are very easily oxidized during senescence to yield several isomeric allylic 9-hydroperoxides. Elucidation of the electron ionization mass spectrometry (EIMS) fragmentation pathways of the trimethylsilyl (TMS) derivatives of the alcohols (obtained by reduction of the corresponding 9-hydroperoxides) is essential for their characterization and quantification in natural samples. EIMS fragmentation pathways of TMS derivatives of isomeric allylic alcohols resulting from NaBH4 reduction of photo- and autoxidation products of HBI alkenes were investigated. These pathways were deduced by: (i) low-energy collision-induced dissociation gas chromatography/tandem mass spectrometry (CID-GC/MS/MS) and (ii) deuterium labelling. CID-MS/MS analyses and deuterium labelling allowed us to elucidate EIMS fragmentations of TMS derivatives of several isomeric allylic alcohols resulting from NaBH4 reduction of HBI alkene oxidation products and to propose some specific fragment ions for differentiating individual isomers. As an application of some of the described fragmentations, these oxidized compounds in phytoplanktonic cells collected from the Antarctic were characterized and quantified in multiple reaction monitoring (MRM) mode. EIMS fragmentations of TMS derivatives of several isomeric allylic alcohols resulting from NaBH4 reduction of HBI alkene oxidation products are shown to be strongly dependent on the position and configuration of double bonds, allowing simple, yet robust differentiation of individual isomers in natural samples. Copyright © 2014 John Wiley & Sons, Ltd.

  3. Conversion of 1-alkenes into 1,4-diols through an auxiliary-mediated formal homoallylic C–H oxidation

    PubMed Central

    Ghavtadze, Nugzar; Melkonyan, Ferdinand S.; Gulevich, Anton V.; Huang, Chunhui; Gevorgyan, Vladimir

    2014-01-01

    The ubiquitous nature of C-H bonds in organic molecules makes them attractive as a target for rapid complexity generation, but brings with it the problem of achieving selective reactions. In developing new methodology for C-H functionalization, alkenes are an attractive starting material due to their abundance and low cost. Here we describe the conversion of 1-alkenes into 1,4-diols. The method involves the installation of a Si,N-type chelating auxiliary group on the alkene followed by iridium catalyzed C-H silylation of an unactivated δ-C(sp3)-H bond to produce an silolane intermediate. Oxidation of the C-Si bonds affords a 1,4-diol. The method is demonstrated to have broad scope and a good functional group compatibility by application to the selective 1,4-oxygenation of several natural products and derivatives. PMID:24451587

  4. Conversion of 1-alkenes into 1,4-diols through an auxiliary-mediated formal homoallylic C-H oxidation.

    PubMed

    Ghavtadze, Nugzar; Melkonyan, Ferdinand S; Gulevich, Anton V; Huang, Chunhui; Gevorgyan, Vladimir

    2014-02-01

    The ubiquitous nature of C-H bonds in organic molecules makes them attractive as a target for rapid complexity generation, but brings with it the problem of achieving selective reactions. In developing new methodologies for C-H functionalization, alkenes are an attractive starting material because of their abundance and low cost. Here we describe the conversion of 1-alkenes into 1,4-diols. The method involves the installation of a new Si,N-type chelating auxiliary group on the alkene followed by iridium-catalysed C-H silylation of an unactivated δ-C(sp(3))-H bond to produce a silolane intermediate. Oxidation of the C-Si bonds affords a 1,4-diol. The method is demonstrated to have broad scope and good functional group compatibility by application to the selective 1,4-oxygenation of several natural products and derivatives.

  5. Stereoselective Synthesis of cis-2,5-Disubstituted Pyrrolidines via Wacker-Type Aerobic Oxidative Cyclization of Alkenes with tBu-Sulfinamide Nucleophiles

    PubMed Central

    Redford, Joanne E.; McDonald, Richard I.; Rigsby, Matthew L.; Wiensch, Joshua D.

    2012-01-01

    Palladium(II)-catalyzed aerobic oxidative cyclization of alkenes with tethered tert-butanesulfinamides furnishes enantiopure 2,5-disubstituted pyrrolidines, originating from readily available and easily diversified starting materials. These reactions are the first reported examples of metal-catalyzed addition of sulfinamide nucleophiles to alkenes. PMID:22352383

  6. Overcoming the Gas-Liquid Mass Transfer of O₂ by Means of Photosynthetic Water Oxidation Coupled with Biocatalytic Oxyfunctionalization.

    PubMed

    Hoschek, Anna; Bühler, Bruno; Schmid, Andreas

    2017-09-25

    Gas-liquid mass transfer of gaseous reactants is a major limitation for high space-time yields, especially for O₂-dependent (bio)catalytic reactions in aqueous solutions. Oxygenic photosynthesis was used for homogeneous O₂-supply via in situ generation in the liquid phase to overcome gas-liquid mass transfer limitations. The phototrophic cyanobacterium Synechocystis sp. PCC6803 was engineered to synthesize alkane monooxygenase AlkBGT, originating from Pseudomonas putida GPo1. With light, but without external addition of O₂, the chemo- and regioselective hydroxylation of nonanoic acid methyl ester to ω-hydroxynonanoic acid methyl ester was driven by O₂ generated via photosynthetic water oxidation. Photosynthesis also delivered the necessary reduction equivalents regenerating Fe2+ in AlkB for oxygen transfer to the terminal methyl group. The in situ coupling of oxygenic photosynthesis to O₂-transferring enzymes now allows the design of fast hydrocarbon oxyfunctionalization reactions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Water independent SO2 oxidation by Stabilised Criegee Intermediates from Biogenic Alkenes

    NASA Astrophysics Data System (ADS)

    Newland, Mike; Rickard, Andrew; Vereecken, Luc; Evans, Mat; Muñoz, Amalia; Ródenas, Milagros; Bloss, William

    2015-04-01

    Biogenic VOCs account for about 90% of global VOC emissions and these are dominated by the unsaturated hydrocarbons: isoprene (600 Tg yr-1) and monoterpenes (100 Tg yr-1). Stabilized Criegee Intermediates (SCI) are thought to be formed in the atmosphere mainly from reactions of unsaturated hydrocarbons with ozone. SCI have been shown in laboratory experiments to rapidly oxidise SO2 (k > 2x10-11 cm3 s-1) and NO2 (k = 7x10-12 cm3 s-1), providing a potentially important gas phase oxidation route for these species in the atmosphere. The importance of the SCI reaction with traces gases has been shown in modelling work to be critically dependent on the ratio of the rate constants for the reaction of the SCI with these trace gases and with H2O. Such modelling work has suggested that the SCI + SO2 reaction is only likely to be important in regions with high alkene emissions, e.g. forests, and that elsewhere SCI are likely to be almost entirely quenched by reaction with water, thus negating their importance as trace gas oxidants. However, it has been shown in laboratory experiments with small SCI that the reaction rate of SCI with water is structure dependent, with anti-CH3CHOO reacting fast with H2O (k > 1x10-14 cm3 s-1), and syn-CH3CHOO reacting orders of magnitude slower (k < 2x10-16 cm3 s-1). Here we present results from a series of ozonolysis experiments performed at the EUPHORE atmospheric simulation chamber in Valencia. These experiments measure the loss of SO2, in the presence of various biogenic alkenes (isoprene and three monoterpenes: α-pinene, β-pinene and limonene), as a function of water vapour. The SO2 loss shows a dependence on relative humidity for all systems studied, decreasing with increasing relative humidity. However, for all species, there also appears to be a fraction of the SO2 loss that shows a much lower sensitivity to relative humidity. We quantify the relative rates of reaction of the SCI produced in the ozonolysis of these biogenics with

  8. Anaerobic oxidation of n-alkenes by sulphate-reducing bacteria from the genus Desulfatiferula: n-ketones as potential metabolites.

    PubMed

    Grossi, Vincent; Cravo-Laureau, Cristiana; Rontani, Jean-François; Cros, Magali; Hirschler-Réa, Agnès

    2011-11-01

    Two alkene-degrading sulphate-reducing bacteria from the genus Desulfatiferula (Desulfatiferula olefinivorans strain LM2801(T) and Desulfatiferula sp. strain BE2801) were investigated for their 1-alkene metabolism. Their total cellular fatty acids were predominantly C-even when they were grown on C-even 1-alkene (1-hexadecene), whereas a mixture of fatty acids with C-odd or C-even carbon chains predominated when cells were grown on C-odd 1-alkene (1-pentadecene). This is consistent with the fatty acid composition of other sulphate-reducing strains previously reported to grow on n-alkenes. Linear and 3-OH-fatty acids appear to be the main fatty acids produced by the two Desulfatiferula strains. The analysis of their neutral lipids led to identifying several n-alkanols and n-ketones with the same number of carbon atoms as the alkene growth substrate and with functionality located between C-1 and C-5. Growth of strains LM2801(T) and BE2801 on (per) deuterated 1-alkenes provided direct evidence of their anaerobic transformation to corresponding 1-alkanols, n-ketones and linear (3-OH-) fatty acids. These results demonstrate that Desulfatiferula strains oxidize a 1-alkene by oxidation of the double bond at C-1, but also at C-2 to C-5 (after eventual isomerization of the double bond) yielding the corresponding C-2 to C-5 n-ketones (via the corresponding n-alkanols). The formation of specific 3-OH-fatty acids by elongation of shorter chain fatty acids was also demonstrated. Based on our observations, pathways for anaerobic 1-alkene metabolism in sulphate-reducing bacteria from the genus Desulfatiferula are proposed. They indicate that n-ketones can constitute new metabolites of the biodegradation of n-alkenes in anaerobic environments. Copyright © 2011 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

  9. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase

    SciTech Connect

    Carlin, DA; Bertolani, SJ; Siegel, JB

    2015-01-01

    Mutants of toluene o-xylene monooxygenase are demonstrated to oxidize ethylene to ethylene oxide in vivo at yields of >99%. The best mutant increases ethylene oxidation activity by >5500-fold relative to the native enzyme. This is the first report of a recombinant enzyme capable of carrying out this industrially significant chemical conversion.

  10. Biocatalytic conversion of ethylene to ethylene oxide using an engineered toluene monooxygenase.

    PubMed

    Carlin, D A; Bertolani, S J; Siegel, J B

    2015-02-11

    Mutants of toluene o-xylene monooxygenase are demonstrated to oxidize ethylene to ethylene oxide in vivo at yields of >99%. The best mutant increases ethylene oxidation activity by >5500-fold relative to the native enzyme. This is the first report of a recombinant enzyme capable of carrying out this industrially significant chemical conversion.

  11. Biocatalytic oxidation of polycyclic aromatic hydrocarbons by hemoglobin and hydrogen peroxide.

    PubMed

    Ortiz-Leon, M; Velasco, L; Vazquez-Duhalt, R

    1995-10-24

    Hemoglobin is able to oxidize polycyclic aromatic hydrocarbons, PAH's, in presence of hydrogen peroxide. Among 12 aromatic compounds tested, six were oxidized; anthracene, carbazole, dibenzothiophene, fluorene, 9-hexylanthracene and pyrene. The products were identified as aromatic ketones and sulfoxides. Effect of organic solvent concentration and hemoglobin stability were determined.

  12. Stereoselective Formation of Substituted 1,3-Dioxolanes through a Three-Component Assembly during the Oxidation of Alkenes with Hypervalent Iodine(III).

    PubMed

    Shimogaki, Mio; Fujita, Morifumi; Sugimura, Takashi

    2015-09-17

    Stereoselective formation of substituted 1,3-dioxolanes was achieved through an assembly of three components: alkene, carboxylic acid and silyl enol ether. The reaction proceeded via stereospecific generation of a 1,3-dioxolan-2-yl cation intermediate during oxidation of alkene substrates with hypervalent iodine. The stereoselective trapping of the cation intermediate with silyl enol ether completed the formation of the dioxolane product.

  13. Biocatalytic Dynamic Kinetic Resolution for the Synthesis of Atropisomeric Biaryl N-Oxide Lewis Base Catalysts.

    PubMed

    Staniland, Samantha; Adams, Ralph W; McDouall, Joseph J W; Maffucci, Irene; Contini, Alessandro; Grainger, Damian M; Turner, Nicholas J; Clayden, Jonathan

    2016-08-26

    Atropisomeric biaryl pyridine and isoquinoline N-oxides were synthesized enantioselectively by dynamic kinetic resolution (DKR) of rapidly racemizing precursors exhibiting free bond rotation. The DKR was achieved by ketoreductase (KRED) catalyzed reduction of an aldehyde to form a configurationally stable atropisomeric alcohol, with the substantial increase in rotational barrier arising from the loss of a bonding interaction between the N-oxide and the aldehyde. Use of different KREDs allowed either the M or P enantiomer to be synthesized in excellent enantiopurity. The enantioenriched biaryl N-oxide compounds catalyze the asymmetric allylation of benzaldehyde derivatives with allyltrichlorosilane.

  14. Non-hazardous biocatalytic oxidation in Nylon-9 monomer synthesis on a 40 g scale with efficient downstream processing.

    PubMed

    Milker, Sofia; Fink, Michael J; Rudroff, Florian; Mihovilovic, Marko D

    2017-08-01

    This paper describes the development of a biocatalytic process on the multi-dozen gram scale for the synthesis of a precursor to Nylon-9, a specialty polyamide. Such materials are growing in demand, but their corresponding monomers are often difficult to synthesize, giving rise to biocatalytic approaches. Here, we implemented cyclopentadecanone monooxygenase as an Escherichia coli whole-cell biocatalyst in a defined medium, together with a substrate feeding-product removal concept, and an optimized downstream processing (DSP). A previously described hazardous peracid-mediated oxidation was thus replaced with a safe and scalable protocol, using aerial oxygen as oxidant, and water as reaction solvent. The engineered process converted 42 g (0.28 mol) starting material ketone to the corresponding lactone with an isolated yield of 70% (33 g), after highly efficient DSP with 95% recovery of the converted material, translating to a volumetric yield of 8 g pure product per liter. Biotechnol. Bioeng. 2017;114: 1670-1678. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  15. Amination of ω-Functionalized Aliphatic Primary Alcohols by a Biocatalytic Oxidation-Transamination Cascade.

    PubMed

    Pickl, Mathias; Fuchs, Michael; Glueck, Silvia M; Faber, Kurt

    2015-10-01

    Amination of non-activated aliphatic fatty alcohols to the corresponding primary amines was achieved through a five-enzyme cascade reaction by coupling a long-chain alcohol oxidase from Aspergillus fumigatus (LCAO_Af) with a ω-transaminase from Chromobacterium violaceum (ω-TA_Cv). The alcohol was oxidized at the expense of molecular oxygen to yield the corresponding aldehyde, which was subsequently aminated by the PLP-dependent ω-TA to yield the final primary amine product. The overall cascade was optimized with respect to pH, O2 pressure, substrate concentration, decomposition of H2O2 (derived from alcohol oxidation), NADH regeneration, and biocatalyst ratio. The substrate scope of this concept was investigated under optimized conditions by using terminally functionalized C4-C11 fatty primary alcohols bearing halogen, alkyne, amino, hydroxy, thiol, and nitrile groups.

  16. Enhanced Biocatalytic Esterification with Lipase-Immobilized Chitosan/Graphene Oxide Beads

    PubMed Central

    Lau, Siaw Cheng; Lim, Hong Ngee; Basri, Mahiran; Fard Masoumi, Hamid Reza; Ahmad Tajudin, Asilah; Huang, Nay Ming; Pandikumar, Alagarsamy; Chia, Chi Hua; Andou, Yoshito

    2014-01-01

    In this work, lipase from Candida rugosa was immobilized onto chitosan/graphene oxide beads. This was to provide an enzyme-immobilizing carrier with excellent enzyme immobilization activity for an enzyme group requiring hydrophilicity on the immobilizing carrier. In addition, this work involved a process for the preparation of an enzymatically active product insoluble in a reaction medium consisting of lauric acid and oleyl alcohol as reactants and hexane as a solvent. This product enabled the stability of the enzyme under the working conditions and allowed the enzyme to be readily isolated from the support. In particular, this meant that an enzymatic reaction could be stopped by the simple mechanical separation of the “insoluble” enzyme from the reaction medium. Chitosan was incorporated with graphene oxide because the latter was able to enhance the physical strength of the chitosan beads by its superior mechanical integrity and low thermal conductivity. The X-ray diffraction pattern showed that the graphene oxide was successfully embedded within the structure of the chitosan. Further, the lipase incorporation on the beads was confirmed by a thermo-gravimetric analysis. The lipase immobilization on the beads involved the functionalization with coupling agents, N-hydroxysulfosuccinimide sodium (NHS) and 1-ethyl-(3-dimethylaminopropyl) carbodiimide (EDC), and it possessed a high enzyme activity of 64 U. The overall esterification conversion of the prepared product was 78% at 60°C, and it attained conversions of 98% and 88% with commercially available lipozyme and novozyme, respectively, under similar experimental conditions. PMID:25127038

  17. The use of microscale processing technologies for quantification of biocatalytic Baeyer-Villiger oxidation kinetics.

    PubMed

    Doig, Steven D; Pickering, Samuel C R; Lye, Gary J; Woodley, John M

    2002-10-05

    Microscale processing techniques would be a useful tool for the rapid and efficient collection of biotransformation kinetic data as a basis for bioprocess design. Automated liquid handling systems can reduce labor intensity while the small scale reduces the demand for scarce materials such as substrate, product, and biocatalyst. Here we illustrate this concept by establishing the use of several microwell formats (96-round, 96-deep square and 24-round well microtiter plates) for quantification of the kinetics of the E. coli TOP10 [pQR239] resting cell catalyzed Baeyer-Villiger oxidation of bicyclo[3.2.0]hept-2en-6-one using glycerol as a source of reducing power. By increasing the biocatalyst concentration until the biotransformation rate was oxygen mass-transfer limited we can ensure that kinetic data collected are in the region away from oxygen limitation. Using a 96-round well plate the effect of substrate (bicyclo[3.2.0]hept-2en-6-one) concentration on the volumetric CHMO activity was examined and compared to data collected from 1.5-L stirred-tank experiments. The phenomenon and magnitude of substrate inhibition, observed at the larger scale, was accurately reproduced in the microwell format. We have used this as an illustrative example to demonstrate that under adequately defined conditions, automated microscale processing technologies can be used for the collection of quantitative kinetic data. Additionally, by using the experimentally determined stoichiometry for product formation and glycerol oxidation, we have estimated the maximum oxygen transfer rates as a function of well geometry and agitation rate. Oxygen-transfer rates with an upper limit of between 33 mmol. L(-1). h(-1) (based solely on product formation) and 390 mmol. L(-1). h(-1) (based on product formation and glycerol oxidation) were achieved using a 96-square well format plate shaken at 1300 rpm operated with a static surface area to volume ratio of 320 m(2). m(-3).

  18. Biocatalytic oxidation of bisphenol A in a reverse micelle system using horseradish peroxidase.

    PubMed

    Hong-Mei, Li; Nicell, James A

    2008-07-01

    Horseradish peroxidase (HRP) was used to catalyze the oxidation of bisphenol A (BPA) in a reverse micelle system consisting of water, sodium bis(2-ethylhexyl)sulfosuccinate (AOT) as the surfactant, and n-octane as the organic solvent phase. In order to achieve maximal BPA transformation, a water-to-surfactant molar ratio greater than 15 was required, above which no further increase in conversion was observed. BPA transformation was catalyzed in the reverse micelle system over a pH range of 6-9 with an optimum at pH 7 and was enhanced with increasing temperatures up to 40 degrees C. The stoichiometric ratio of moles of bisphenol A transformed per mole of peroxide consumed was 0.46 when the initial BPA concentration was 0.01 mM, which is significantly less than the theoretical value of 2 based on the known catalytic cycle of the enzyme. However, the stoichiometric ratio increased and approach the theoretical value with higher BPA concentrations. Over the course of the catalytic reaction, the enzyme became inactivated. Hydrogen peroxide strongly inhibited the enzyme and, thus, when the oxidant was present in quantities in excess of the stoichiometric amount, BPA transformation was significantly reduced.

  19. Palladium-catalyzed oxidative Heck-type alkylation/aryl migration/desulfonylation between alkenes with α-carbonyl alkyl bromides.

    PubMed

    Fan, Jian-Hong; Yang, Ji; Song, Ren-Jie; Li, Jin-Heng

    2015-02-20

    A new Pd(II)-catalyzed alkene oxidative difunctionalization initiated by Heck insertion has been developed for the selective synthesis of acyclic and cyclic all-carbon quaternary stereocenters, which achieves an oxidative Heck-type alkylation, aryl migration, and desulfonylation sequence and represents a different input from those previously used Heck coupling in synthesis is reported.

  20. Distinct rat hepatic microsomal epoxide hydrolases catalyze the hydration of cholesterol 5,6 alpha-oxide and certain xenobiotic alkene and arene oxides.

    PubMed

    Levin, W; Michaud, D P; Thomas, P E; Jerina, D M

    1983-02-01

    Metabolism of cholesterol 5,6 alpha-oxide to the 5,6-glycol is catalyzed by a rat liver microsomal epoxide hydrolase that is distinct from the microsomal epoxide hydrolase that metabolizes a wide range of xenobiotic alkene and arene oxides. The two enzymes are antigenically distinct, and the purified microsomal epoxide hydrolase that metabolizes xenobiotic oxides does not catalyze the hydration of cholesterol 5,6 alpha-oxide. In vivo treatment of rats with inducers of microsomal epoxide hydrolase does not enhance the activity of cholesterol 5,6 alpha-oxide hydrolase and, in some cases, actually depresses enzyme activity in the resultant microsomal preparations. Octene 1,2-oxide and benz[a]anthracene 5,6-oxide, both good substrates for xenobiotic epoxide hydrolase, are not competitive inhibitors of cholesterol oxide hydration by rat liver microsomes. The above results establish the existence of a liver microsomal epoxide hydrolase that is under different regulatory control and that appears to have a different substrate specificity than the well-characterized microsomal epoxide hydrolase involved in the metabolism of a widely diverse group of alkene and arene oxides.

  1. Extending the alkene substrate range of vinyl chloride utilizing Nocardioides sp. strain JS614 with ethene oxide.

    PubMed

    Taylor, Anne E; Arp, Daniel J; Bottomley, Peter J; Semprini, Lewis

    2010-08-01

    Nocardioides sp. strain JS614 grows on the C(2) alkenes ethene (Eth), vinyl chloride, and vinyl fluoride as sole carbon sources. The presence of 400-800 microM ethene oxide (EtO) extended the growth substrate range to propene (C(3)) and butene (C(4)). Propene-dependent growth of JS614 was CO(2) dependent and was prevented by the carboxylase/reductase inhibitor 2-bromoethanesulfonic acid, sodium salt (BES), while growth on Eth was not CO(2) dependent or BES sensitive. Although unable to promote growth, both propene and propene oxide (PrO)-induced expression of the genes encoding the alpha subunit of alkene monooxygenase (etnC) and epoxyethane CoM transferase (etnE) to similar levels as did Eth and EtO. Propene was transformed by Eth-grown and propene-grown/EtO-induced JS614 to PrO at a rate 4.2 times faster than PrO was consumed. As a result PrO accumulated in growth medium to 900 microM during EtO-induced growth on propene. PrO (50-100 microM) exerted inhibitory effects on growth of JS614 on both acetate and Eth, and on EtO-induced growth on Eth. However, higher EtO concentrations (300-400 microM) overcame the negative effects of PrO on Eth-dependent growth.

  2. Cobalt salophen complex supported on imidazole functionalized magnetic nanoparticles as a recoverable catalyst for oxidation of alkenes

    NASA Astrophysics Data System (ADS)

    Afshari, Mozhgan; Gorjizadeh, Maryam; Nazari, Simin; Naseh, Mohammad

    2014-08-01

    A new magnetically separable catalyst consisting of Co(II) salophen complex covalently supported on imidazole functionalized silica coated cobalt ferrite was prepared. The synthesized catalyst was characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), thermogravimetric analysis (TGA), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and Fourier transform infrared (FT-IR). The immobilized catalyst was shown to be an efficient heterogeneous catalyst for the oxidation of some alkenes using hydrogen peroxide (H2O2) as oxidant. The catalyst could be easily and efficiently isolated from the final product solution by magnetic decantation and be reused for 5 consecutive reactions without showing any significant activity degradation.

  3. Aliphatic and chlorinated alkenes and epoxides as inducers of alkene monooxygenase and epoxidase activities in Xanthobacter strain Py2

    SciTech Connect

    Ensign, S.A.

    1996-01-01

    Xanthobacter strain Py2 is one of a number of bacteria capable of aerobic growth using aliphatic alkenes as the sole carbon and energy source. The oxidation of alkenes in initiated by an alkene monooxygenase which catalyzes the CO{sub 2} and reductant-dependent oxidation of the alkenes to their corresponding epoxides. In this study, the induction of the alkene-oxidizing enzymes of Xantheobacter strain Py2 by the physiological substrates propylene and proplyene oxide is characterized. A variety of aliphatic and chlorinated alkenes and epoxides are shown to serve as effective inducers of the system. 21 refs., 6 figs., 2 tabs.

  4. Total synthesis of gracilioether F. Development and application of Lewis acid promoted ketene–alkene [2+2] cycloadditions and late-stage C—H oxidation

    SciTech Connect

    Rasik, Christopher M.; Brown, M. Kevin

    2014-12-22

    The first synthesis of gracilioether F, a polyketide natural product with an unusual tricyclic core and five contiguous stereocenters, is described. Key steps of the synthesis include a Lewis acid promoted ketene–alkene [2+2] cycloaddition and a late-stage carboxylic acid directed C(sp³)—H oxidation. The synthesis requires only eight steps from norbornadiene.

  5. Binding of alkenes and ionic liquids to B-H-functionalized boron nanoparticles: creation of particles with controlled dispersibility and minimal surface oxidation.

    PubMed

    Perez, Jesus Paulo L; Yu, Jiang; Sheppard, Anna J; Chambreau, Steven D; Vaghjiani, Ghanshyam L; Anderson, Scott L

    2015-05-13

    The interaction of B-H-functionalized boron nanoparticles with alkenes and nitrogen-rich ionic liquids (ILs) is investigated by a combination of X-ray photoelectron spectroscopy, FTIR spectroscopy, dynamic light scattering, thermogravimetric analysis, and helium ion microscopy. Surface B-H bonds are shown to react with terminal alkenes to produce alkyl-functionalized boron particles. The interaction of nitrogen-rich ILs with the particles appears, instead, to be dominated by boron-nitrogen bonding, even for an ILs with terminal alkene functionality. This chemistry provides a convenient approach to producing and capping boron nanoparticles with a protective organic layer, which is shown to protect the particles from oxidation during air exposure. By controlling the capping group, particles with high dispersibility in nonpolar or polar liquids can be produced. For the particles capped with ILs, the effect of particle loading on hypergolic ignition of the ILs is reported.

  6. Cometabolic degradation of chlorinated alkenes by alkene monooxygenase in a propylene-grown Xanthobacter strain.

    PubMed Central

    Ensign, S A; Hyman, M R; Arp, D J

    1992-01-01

    Propylene-grown Xanthobacter cells (strain Py2) degraded several chlorinated alkenes of environmental concern, including trichloroethylene, 1-chloroethylene (vinyl chloride), cis- and trans-1,2-dichloroethylene, 1,3-dichloropropylene, and 2,3-dichloropropylene. 1,1-Dichloroethylene was not degraded efficiently, while tetrachloroethylene was not degraded. The role of alkene monooxygenase in catalyzing chlorinated alkene degradations was established by demonstrating that glucose-grown cells which lack alkene monooxygenase and propylene-grown cells in which alkene monooxygenase was selectively inactivated by propyne were unable to degrade the compounds. C2 and C3 chlorinated alkanes were not oxidized by alkene monooxygenase, but a number of these compounds were inhibitors of propylene and ethylene oxidation, suggesting that they compete for binding to the enzyme. A number of metabolites enhanced the rate of degradation of chlorinated alkenes, including propylene oxide, propionaldehyde, and glucose. Propylene stimulated chlorinated alkene oxidation slightly when present at a low concentration but became inhibitory at higher concentrations. Toxic effects associated with chlorinated alkene oxidations were determined by measuring the propylene oxidation and propylene oxide-dependent O2 uptake rates of cells previously incubated with chlorinated alkenes. Compounds which were substrates for alkene monooxygenase exhibited various levels of toxicity, with 1,1-dichloroethylene and trichloroethylene being the most potent inactivators of propylene oxidation and 1,3- and 2,3-dichloropropylene being the most potent inactivators of propylene oxide-dependent O2 uptake. No toxic effects were seen when cells were incubated with chlorinated alkenes anaerobically, indicating that the product(s) of chlorinated alkene oxidation mediates toxicity. PMID:1444418

  7. Ozonolysis of surface adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2013-07-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (±0.8) × 10-7 and 2 (±1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ>300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(±1) but had no effect on ozonolysis of the alkene side-chain.

  8. Self-assembled monolayers of 1-alkenes on oxidized platinum surfaces as platforms for immobilized enzymes for biosensing

    NASA Astrophysics Data System (ADS)

    Alonso, Jose Maria; Bielen, Abraham A. M.; Olthuis, Wouter; Kengen, Servé W. M.; Zuilhof, Han; Franssen, Maurice C. R.

    2016-10-01

    Alkene-based self-assembled monolayers grafted on oxidized Pt surfaces were used as a scaffold to covalently immobilize oxidase enzymes, with the aim to develop an amperometric biosensor platform. NH2-terminated organic layers were functionalized with either aldehyde (CHO) or N-hydroxysuccinimide (NHS) ester-derived groups, to provide anchoring points for enzyme immobilization. The functionalized Pt surfaces were characterized by X-ray photoelectron spectroscopy (XPS), static water contact angle (CA), infrared reflection absorption spectroscopy (IRRAS) and atomic force microscopy (AFM). Glucose oxidase (GOX) was covalently attached to the functionalized Pt electrodes, either with or without additional glutaraldehyde crosslinking. The responses of the acquired sensors to glucose concentrations ranging from 0.5 to 100 mM were monitored by chronoamperometry. Furthermore, lactate oxidase (LOX) and human hydroxyacid oxidase (HAOX) were successfully immobilized onto the PtOx surface platform. The performance of the resulting lactate sensors was investigated for lactate concentrations ranging from 0.05 to 20 mM. The successful attachment of active enzymes (GOX, LOX and HAOX) on Pt electrodes demonstrates that covalently functionalized PtOx surfaces provide a universal platform for the development of oxidase enzyme-based sensors.

  9. Hydration of arene and alkene oxides by epoxide hydrase in human liver microsomes.

    PubMed

    Kapitulnik, J; Levin, W; Morecki, R; Dansette, P M; Jerina, D M; Conney, A H

    1977-02-01

    The comparative hydration of styrene 7,8-oxide, octene 1,2-oxide, naphthalene 1,2-oxide, phenanthrene 9,10-oxide, benzo[a]anthracene 5,6-oxide, 3-methylcholanthrene 11,12-oxide, dibenzo[a,h]anthracene 5,6-oxide, and benzo[a, 7,8-, 9,10-, and 11,12-oxides to their respective dihydrodiols was investigated in microsomes from nine human autopsy livers. The substrate specificity of the epoxide hydrase in human liver microsomes was very similar to that of the epoxide hydrase in rat liver microsomes. Phenanthrene 9,10-oxide was the best substrate for the human and rat epoxide hydrases and dibenzo[a,h]anthracene 5,6-oxide and benzo[a-a)pyrene 11, 12-oxide were the poorest substrates. Plotting epoxide hydrase activity obtained with one substrate against epoxide hydrase activity for another substrate for each of the nine human livers revealed excellent correlations for all combinations of the 11 substrates studied (r = 0.87 to 0.99). The data suggest the presence in human liver of a single epoxide hydrase with broad substrate specificity. However, the results do not exclude the possible presence in human liver of several epoxide hydrases that are under similar regulatory control. These results suggest the need for further investigation to determine whether there is a safe epoxide of a drug whose in vivo metabolism is predictive of the capacity of different individuals to metabolize a wide variety of epoxides of drugs and environmental chemicals.

  10. Investigating the oxidation of alkenes by non-heme iron enzyme mimics.

    PubMed

    Barry, Sarah M; Mueller-Bunz, Helge; Rutledge, Peter J

    2012-09-28

    Iron is emerging as a key player in the search for efficient and environmentally benign methods for the functionalisation of C-H bonds. Non-heme iron enzymes catalyse a diverse array of oxidative chemistry in nature, and small-molecule complexes designed to mimic the non-heme iron active site have great potential as C-H activation catalysts. Herein we report the synthesis of a series of organic ligands that incorporate key features of the non-heme iron active site. Iron(II) complexes of these ligands have been generated in situ and their ability to promote hydrocarbon oxidation has been investigated. Several of these systems promote the biomimetic dihydroxylation of cyclohexene at low levels, when hydrogen peroxide is used as the oxidant; allylic oxidation products are also observed. An investigation of ligand stability reveals formation of several breakdown products under the conditions of the oxidative turnover reactions. These products arise via oxidative decarboxylation, dehydration and deamination reactions. Taken together these results indicate that competing mechanisms are at play with these systems: biomimetic hydroxylation involving high-valent iron species, and allylic oxidation via Fenton chemistry and Haber-Weiss radical pathways.

  11. PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)

    EPA Science Inventory

    The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

  12. PALLADIUM-CATALYZED OXIDATION OF STYRENE AND ALKENES IN PRESENCE OF IONIC LIQUIDS (WACKER REACTION)

    EPA Science Inventory

    The use of ionic liquids in various synthetic transformations is gaining significance due to the enhanced reaction rates, potential for recycling and compatibility with various organic compounds and organometallic catalysts. Palladium-catalyzed oxidation of styrene and other alk...

  13. Enantioselective Pd(II)-catalyzed aerobic oxidative amidation of alkenes and insights into the role of electronic asymmetry in pyridine-oxazoline ligands.

    PubMed

    McDonald, Richard I; White, Paul B; Weinstein, Adam B; Tam, Chun Pong; Stahl, Shannon S

    2011-06-03

    Enantioselective intramolecular oxidative amidation of alkenes has been achieved using a (pyrox)Pd(II)(TFA)(2) catalyst (pyrox = pyridine-oxazoline, TFA = trifluoroacetate) and O(2) as the sole stoichiometric oxidant. The reactions proceed at room temperature in good-to-excellent yields (58-98%) and with high enantioselectivity (ee = 92-98%). Catalyst-controlled stereoselective cyclization reactions are demonstrated for a number of chiral substrates. DFT calculations suggest that the electronic asymmetry of the pyrox ligand synergizes with steric asymmetry to control the stereochemical outcome of the key amidopalladation step.

  14. Enantioselective Pd(II)-Catalyzed Aerobic Oxidative Amidation of Alkenes and Insights into the Role of Electronic Asymmetry in Pyridine-Oxazoline Ligands

    PubMed Central

    McDonald, Richard I.; White, Paul B.; Weinstein, Adam B.; Tam, Chun Pong; Stahl, Shannon S.

    2011-01-01

    Enantioselective intramolecular oxidative amidation of alkenes has been achieved using a (pyrox)Pd(II)(TFA)2 catalyst (pyrox = pyridine-oxazoline, TFA = trifluoroacetate) and O2 as the sole stoichiometric oxidant. The reactions proceed at room temperature in good-to-excellent yield (58-98%) and with high enantioselectivity (ee = 92-98%). Catalyst-controlled stereoselective cyclization reactions are demonstrated for a number of chiral substrates. DFT calculations suggest that the electronic asymmetry of the pyrox ligand synergizes with steric asymmetry to control the stereochemical outcome of the key amidopalladation step. PMID:21534607

  15. Palladium-Catalyzed Oxidative Arylhalogenation of Alkenes: Synthetic Scope and Mechanistic Insights

    PubMed Central

    Kalyani, Dipannita; Satterfield, Andrew D.

    2010-01-01

    This article describes the development of a Pd-catalyzed reaction for the arylhalogenation (halogen = Cl or Br) of diverse α-olefins by oxidatively intercepting Mizoroki-Heck intermediates. These transformations afford synthetically useful 1,2- and 1,1-arylhalogenated products in good yields with good to excellent selectivities that can be modulated by changing the nature of the halogenating reagent and/or the reaction conditions. The selectivity of these reactions can be rationally tuned by: (i) controlling the relative rates of oxidative functionalization versus β-hydride elimination from equilibrating PdII-alkyl species and (ii) stabilization of organometallic PdII intermediates through the formation of π-benzyl adducts. These arylhalogenations exhibit modest to excellent levels of stereospecificity, and the key carbon-halogen bond-forming step proceeds with predominant retention of stereochemistry at carbon. PMID:20515033

  16. Biocatalytic portfolio of Basidiomycota.

    PubMed

    Schmidt-Dannert, Claudia

    2016-04-01

    Basidiomycota fungi have received little attention for applications in biocatalysis and biotechnology and remain greatly understudied despite their importance for carbon recycling, ecosystem functioning and medicinal properties. The steady influx of genome data has facilitated detailed studies aimed at understanding the evolution and function of fungal lignocellulose degradation. These studies and recent explorations into the secondary metabolomes have uncovered large portfolios of enzymes useful for biocatalysis and biosynthesis. This review will provide an overview of the biocatalytic repertoires of Basidiomycota characterized to date with the hope of motivation more research into the chemical toolkits of this diverse group of fungi.

  17. Selective oxidation of alkanes and/or alkenes to valuable oxygenates

    DOEpatents

    Lin, Manhua; Pillai, Krishnan S.

    2011-02-15

    A catalyst, its method of preparation and its use for producing at least one of methacrolein and methacrylic acid, for example, by subjecting isobutane or isobutylene or a mixture thereof to a vapor phase catalytic oxidation in the presence of air or oxygen. In the case where isobutane alone is subjected to a vapor phase catalytic oxidation in the presence of air or oxygen, the product is at least one of isobutylene, methacrolein and methacrylic acid. The catalyst comprises a compound having the formula A.sub.aB.sub.bX.sub.xY.sub.yZ.sub.zO.sub.o wherein A is one or more elements selected from the group of Mo, W and Zr, B is one or more elements selected from the group of Bi, Sb, Se, and Te, X is one or more elements selected from the group of Al, Bi, Ca, Ce, Co, Fe, Ga, Mg, Ni, Nb, Sn, W and Zn, Y is one or more elements selected from the group of Ag, Au, B, Cr, Cs, Cu, K, La, Li, Mg, Mn, Na, Nb, Ni, P, Pb, Rb, Re, Ru, Sn, Te, Ti, V and Zr, and Z is one or more element from the X or Y groups or from the following: As, Ba, Pd, Pt, Sr, or mixtures thereof, and wherein a=1, 0.05oxidation state of the other elements.

  18. Copper-Catalyzed Oxidative Dehydrogenative Carboxylation of Unactivated Alkanes to Allylic Esters via Alkenes

    PubMed Central

    2015-01-01

    We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV–vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C–H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C–H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper–carboxylate, copper–amidate, and copper–imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)–amidate > Cu(II)–imidate > Cu(II)–benzoate. Consistent with this trend, Cu(II)–amidates and Cu(II)–benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products. PMID:25389772

  19. Polar Addition to C=C Group: Why Is Anti-Markovnikov Hydroboration-Oxidation of Alkenes Not "Anti-"?

    ERIC Educational Resources Information Center

    Ilich, Predrag-Peter; Rickertsen, Lucas S.; Becker, Erienne

    2006-01-01

    For 137 years Markovnikov's rule has been extensively used in organic chemical education and research to describe the regioselectivity in electrophilic addition reactions to alkenes and alkynes. When the structures of the final reaction products are used as reference, the rule requests that certain polar addition reactions be termed…

  20. Keap1 perceives stress via three sensors for the endogenous signaling molecules nitric oxide, zinc, and alkenals.

    PubMed

    McMahon, Michael; Lamont, Douglas J; Beattie, Kenneth A; Hayes, John D

    2010-11-02

    Recognition and repair of cellular damage is crucial if organisms are to survive harmful environmental conditions. In mammals, the Keap1 protein orchestrates this response, but how it perceives adverse circumstances is not fully understood. Herein, we implicate NO, Zn(2+), and alkenals, endogenously occurring chemicals whose concentrations increase during stress, in this process. By combining molecular modeling with phylogenetic, chemical, and functional analyses, we show that Keap1 directly recognizes NO, Zn(2+), and alkenals through three distinct sensors. The C288 alkenal sensor is of ancient origin, having evolved in a common ancestor of bilaterans. The Zn(2+) sensor minimally comprises H225, C226, and C613. The most recent sensor, the NO sensor, emerged coincident with an expansion of the NOS gene family in vertebrates. It comprises a cluster of basic amino acids (H129, K131, R135, K150, and H154) that facilitate S-nitrosation of C151. Taken together, our data suggest that Keap1 is a specialized sensor that quantifies stress by monitoring the intracellular concentrations of NO, Zn(2+), and alkenals, which collectively serve as second messengers that may signify danger and/or damage.

  1. Metal-free oxidative hydroxyalkylarylation of activated alkenes by direct sp3 C-H functionalization of alcohols.

    PubMed

    Meng, Yuan; Guo, Li-Na; Wang, Hua; Duan, Xin-Hua

    2013-09-04

    A metal-free tandem radical addition/cyclization reaction of activated alkenes and alcohols has been developed. The process provides an efficient and atom economical access to various valuable hydroxyl-containing oxindoles through the direct sp(3) C-H functionalization of alcohols.

  2. Polar Addition to C=C Group: Why Is Anti-Markovnikov Hydroboration-Oxidation of Alkenes Not "Anti-"?

    ERIC Educational Resources Information Center

    Ilich, Predrag-Peter; Rickertsen, Lucas S.; Becker, Erienne

    2006-01-01

    For 137 years Markovnikov's rule has been extensively used in organic chemical education and research to describe the regioselectivity in electrophilic addition reactions to alkenes and alkynes. When the structures of the final reaction products are used as reference, the rule requests that certain polar addition reactions be termed…

  3. Toluene Monooxygenase-Catalyzed Epoxidation of Alkenes

    PubMed Central

    McClay, Kevin; Fox, Brian G.; Steffan, Robert J.

    2000-01-01

    Several toluene monooxygenase-producing organisms were tested for their ability to oxidize linear alkenes and chloroalkenes three to eight carbons long. Each of the wild-type organisms degraded all of the alkenes that were tested. Epoxides were produced during the oxidation of butene, butadiene, and pentene but not hexene or octadiene. A strain of Escherichia coli expressing the cloned toluene-4-monooxygenase (T4MO) of Pseudomonas mendocina KR1 was able to oxidize butene, butadiene, pentene, and hexene but not octadiene, producing epoxides from all of the substrates that were oxidized. A T4MO-deficient variant of P. mendocina KR1 oxidized alkenes that were five to eight carbons long, but no epoxides were detected, suggesting the presence of multiple alkene-degrading enzymes in this organism. The alkene oxidation rates varied widely (ranging from 0.01 to 0.33 μmol of substrate/min/mg of cell protein) and were specific for each organism-substrate pair. The enantiomeric purity of the epoxide products also varied widely, ranging from 54 to >90% of a single epoxide enantiomer. In the absence of more preferred substrates, such as toluene or alkenes, the epoxides underwent further toluene monooxygenase-catalyzed transformations, forming products that were not identified. PMID:10788354

  4. Oxidation of alkane and alkene moieties with biologically inspired nonheme iron catalysts and hydrogen peroxide: from free radicals to stereoselective transformations.

    PubMed

    Olivo, Giorgio; Cussó, Olaf; Borrell, Margarida; Costas, Miquel

    2017-04-01

    The selective oxidation of hydrocarbons is a challenging reaction for synthetic chemists, but common in nature. Iron oxygenases activate the O-O bond of dioxygen to perform oxidation of alkane and alkenes moieties with outstanding levels of regio-, chemo- and stereoselectivity. Along a bioinspired approach, iron coordination complexes which mimic structural and reactivity aspects of the active sites of nonheme iron oxygenases have been explored as oxidation catalysts. This review describes the evolution of this research field, from the early attempts to reproduce the basic reactivity of nonheme iron oxygenases to the development of effective iron oxidation catalysts. The work covers exclusively nonheme iron complexes which rely on H2O2 or O2 as terminal oxidants. First, it delineates the key steps and the essential catalyst design principles required to activate the peroxide bond at nonheme iron centers without (or at least minimizing) the release of free-diffusing radicals. It follows with a critical description of the mechanistic pathways which govern the reaction between iron complexes and H2O2 to generate the oxidizing species. Eventually, the work presents a state-of-the-art report on the use of these catalysts in aliphatic C-H oxidation, olefin epoxidation and alkene syn-dihydroxylation, under substrate-limiting conditions. A special focus is given on the main strategies elaborated to tune catalyst activity and selectivity by modification of its structure. The work is concluded by a concise discussion on the essential progresses of these oxidation catalysts together with the challenges that remain still to be tackled.

  5. In vitro oxidative decarboxylation of free fatty acids to terminal alkenes by two new P450 peroxygenases.

    PubMed

    Xu, Huifang; Ning, Linlin; Yang, Wenxia; Fang, Bo; Wang, Cong; Wang, Yun; Xu, Jian; Collin, Severine; Laeuffer, Frederic; Fourage, Laurent; Li, Shengying

    2017-01-01

    P450 fatty acid decarboxylases represented by the unusual CYP152 peroxygenase family member OleTJE have been receiving great attention recently since these P450 enzymes are able to catalyze the simple and direct production of 1-alkenes for potential applications in biofuels and biomaterials. To gain more mechanistic insights, broader substrate spectra, and improved decarboxylative activities, it is demanded to discover and investigate more P450 fatty acid decarboxylases. Here, we describe for the first time the expression, purification, and in vitro biochemical characterization of two new CYP152 peroxygenases, CYP-Aa162 and CYP-Sm46Δ29, that are capable of decarboxylating straight-chain saturated fatty acids. Both enzymes were found to catalyze the decarboxylation and hydroxylation of a broad range of free fatty acids (C10-C20) with overlapping substrate specificity, yet distinct chemoselectivity. CYP-Sm46Δ29 works primarily as a fatty (lauric) acid decarboxylase (66.1 ± 3.9% 1-undecene production) while CYP-Aa162 more as a fatty (lauric) acid hydroxylase (72.2 ± 0.9% hydroxy lauric acid production). Notably, the optical spectroscopic analysis of functional CYP-Sm46Δ29 revealed no characteristic P450 band, suggesting a unique heme coordination environment. Active-site mutagenesis analysis showed that substitution with the proposed key decarboxylation-modulating residues, His85 and Ile170, enhanced the decarboxylation activity of CYP-Aa162 and P450BSβ, emphasizing the importance of these residues in directing the decarboxylation pathway. Furthermore, the steady-state kinetic analysis of CYP-Aa162 and CYP-Sm46Δ29 revealed both cooperative and substrate inhibition behaviors which are substrate carbon chain length dependent. Our data identify CYP-Sm46Δ29 as an efficient OleTJE-like fatty acid decarboxylase. Oxidative decarboxylation chemoselectivity of the CYP152 decarboxylases is largely dependent upon the carbon chain length of fatty acid substrates and

  6. Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

    ERIC Educational Resources Information Center

    Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

    2011-01-01

    Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

  7. Oxidation Numbers, Oxidants, and Redox Reactions: Variants of the Electrophilic Bromination of Alkenes and Variants of the Application of Oxone

    ERIC Educational Resources Information Center

    Eissen, Marco; Strudthoff, Merle; Backhaus, Solveig; Eismann, Carolin; Oetken, Gesa; Kaling, Soren; Lenoir, Dieter

    2011-01-01

    Oxidation-state and donor-acceptor concepts are important areas in the chemical education. Student worksheets containing problems that emphasize oxidation numbers, redox reactions of organic compounds, and stoichiometric reaction equations are presented. All of the examples are incorporated under one unifying topic: the production of vicinal…

  8. Electrochemical intramolecular aminooxygenation of unactivated alkenes.

    PubMed

    Xu, Fan; Zhu, Lin; Zhu, Shaobin; Yan, Xiaomei; Xu, Hai-Chao

    2014-09-26

    An electrochemical approach to the intramolecular aminooxygenation of unactivated alkenes has been developed. This process is based on the addition of nitrogen-centered radicals, generated through electrochemical oxidation, to alkenes followed by trapping of the cyclized radical intermediate with 2,2,6,6-tetramethylpiperidine-N-oxyl radical (TEMPO). Difunctionalization of a variety of alkenes with easily available carbamates/amides and TEMPO affords aminooxygenation products in high yields and with excellent trans selectivity for cyclic systems (d.r. up to>20:1). The approach provides a much-needed complementary route to existing cis-selective methods.

  9. Biocatalytic properties of a peroxidase-active cell-free extract from onion solid wastes: caffeic acid oxidation.

    PubMed

    El Agha, Ayman; Abbeddou, Souheila; Makris, Dimitris P; Kefalas, Panagiotis

    2009-04-01

    The exploitation of food residual sources consists of a major factor in reducing the polluting load of food industry wastes and developing novel added-value products. Plant food residues including trimmings and peels might contain a range of enzymes capable of transforming bio-organic molecules with potential phytotoxicity, including hydrolases, peroxidases and polyphenoloxidases. Although the use of bacterial and fungal enzymes has gained interest in studies pertaining to bioremediation applications, plant enzymes have been given less attention or even disregarded. In this view, this study aimed at the investigating the use of a crude peroxidase preparation from onion solid by-products for oxidising caffeic acid, a widespread o-diphenol, whose various derivatives may occur in food industry wastes, such as olive mill waste waters. Increased enzyme activity was observed at a pH value of 5, but considerable activity was also retained for pH up to 7. Favourable temperatures for increased activity varied between 20 degrees C and 40 degrees C, 30 degrees C being the optimal. Liquid chromatography-mass spectrometry analysis of a homogenate/H(2)O(2)-treated caffeic acid solution revealed the existence of a tetramer as major oxidation product. Based on the data generated, a putative pathway for the formation of the peroxidase-mediated caffeic acid tetramer was proposed.

  10. Recombinant Cyanobacteria for the Asymmetric Reduction of C=C Bonds Fueled by the Biocatalytic Oxidation of Water.

    PubMed

    Köninger, Katharina; Gómez Baraibar, Álvaro; Mügge, Carolin; Paul, Caroline E; Hollmann, Frank; Nowaczyk, Marc M; Kourist, Robert

    2016-04-25

    A recombinant enoate reductase was expressed in cyanobacteria and used for the light-catalyzed, enantioselective reduction of C=C bonds. The coupling of oxidoreductases to natural photosynthesis allows asymmetric syntheses fueled by the oxidation of water. Bypassing the addition of sacrificial cosubstrates as electron donors significantly improves the atom efficiency and avoids the formation of undesired side products. Crucial factors for product formation are the availability of NADPH and the amount of active enzyme in the cells. The efficiency of the reaction is comparable to typical whole-cell biotransformations in E. coli. Under optimized conditions, a solution of 100 mg prochiral 2-methylmaleimide was reduced to optically pure 2-methylsuccinimide (99 % ee, 80 % yield of isolated product). High product yields and excellent optical purities demonstrate the synthetic usefulness of light-catalyzed whole-cell biotransformations using recombinant cyanobacteria. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas-wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas-wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  12. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation

    NASA Astrophysics Data System (ADS)

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2015-09-01

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool which explicitly represents SOA formation and gas/wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas/wall mass transfer, the vapor pressure of the species and the duration of the experiments. This work suggests that SOA yields inferred from chamber experiments could be underestimated up to 0.35 yield unit due to the loss of organic vapors to chamber walls.

  13. Biocatalytic material comprising multilayer enzyme coated fiber

    DOEpatents

    Kim, Jungbae [Richland, WA; Kwak, Ja Hun [Richland, WA; Grate, Jay W [West Richland, WA

    2009-11-03

    The present invention relates generally to high stability, high activity biocatalytic materials and processes for using the same. The materials comprise enzyme aggregate coatings having high biocatalytic activity and stability useful in heterogeneous environment. These new materials provide a new biocatalytic immobilized enzyme system with applications in bioconversion, bioremediation, biosensors, and biofuel cells.

  14. Multi-step biocatalytic depolymerization of lignin.

    PubMed

    Picart, Pere; Liu, Haifeng; Grande, Philipp M; Anders, Nico; Zhu, Leilei; Klankermayer, Jürgen; Leitner, Walter; Domínguez de María, Pablo; Schwaneberg, Ulrich; Schallmey, Anett

    2017-08-01

    Lignin is a biomass-derived aromatic polymer that has been identified as a potential renewable source of aromatic chemicals and other valuable compounds. The valorization of lignin, however, represents a great challenge due to its high inherent functionalization, what compromises the identification of chemical routes for its selective depolymerization. In this work, an in vitro biocatalytic depolymerization process is presented, that was applied to lignin samples obtained from beech wood through OrganoCat pretreatment, resulting in a mixture of lignin-derived aromatic monomers. The reported biocracking route comprises first a laccase-mediator system to specifically oxidize the Cα hydroxyl group in the β-O-4 structure of lignin. Subsequently, selective β-O-4 ether cleavage of the oxidized β-O-4 linkages is achieved with β-etherases and a glutathione lyase. The combined enzymatic approach yielded an oily fraction of low-molecular-mass aromatic compounds, comprising coniferylaldehyde and other guaiacyl and syringyl units, as well as some larger (soluble) fractions. Upon further optimization, the reported biocatalytic route may open a valuable approach for lignin processing and valorization under mild reaction conditions.

  15. Asymmetric fluorocyclizations of alkenes.

    PubMed

    Wolstenhulme, Jamie R; Gouverneur, Véronique

    2014-12-16

    .g., TRIP and derivatives) brings into solution the resulting chiral Selectfluor reagent, now capable of asymmetric fluorocyclization. This strategy is best applied to a subset of substrates bearing a nucleophilic pendent group (benzamide is best) capable of hydrogen bonding for association with the chiral phosphate catalyst. These contributions focused on fluoroheterocyclization involving either O- or N-nucleophiles. As for other halocyclizations, alkenes armed with π C-nucleophiles represent the most demanding class of substrates for asymmetric F(+)-induced electrophilic fluorination-cyclization. Successful implementation required the design of new chiral Selectfluor reagents featuring stereogenicity on the DABCO core. These reagents, accessible from chiral vicinal diamines, allowed the synthesis of unusual chiral fluorine-containing tetracyclic compounds, some composed of carbon, hydrogen, and fluorine exclusively. The challenges associated with F(+)-induced fluorocarbocyclizations prompted methodologists to consider chemistry where the Csp(3)-F bond formation event follows a catalyst-controlled cyclization. An exciting development built on in the area of transition metal π-cyclization of polyenes leading to cationic metal-alkyl intermediates. When intercepted by oxidative fluorodemetalation with a F(+) source, the resulting products are complex polycyclic structures emerging from an overall catalytic cascade fluorocarbocyclization. Complementing F(+)-based reactions, examples of fluorocyclizations with fluoride in the presence of an oxidant were reported. Despite some exciting developments, the field of asymmetric fluorocyclizations is in its infancy and undoubtedly requires new activation modes, catalysts, as well as F(+) and F(-) reagents to progress into general retrosynthetic approach toward enantioenriched fluorocycles. Numerous opportunities emerge, not least the use of a latent fluorine source as a means to minimize background fluorination.

  16. Biocatalytic Synthesis of Pikromycin, Methymycin, Neomethymycin, Novamethymycin, and Ketomethymycin

    PubMed Central

    Hansen, Douglas A.; Rath, Christopher M.; Eisman, Eli B.; Narayan, Alison R. H.; Kittendorf, Jeffrey D.; Mortison, Jonathan D.; Yoon°, Yeo Joon; Sherman, David H.

    2013-01-01

    A biocatalytic platform that employs the final two monomodular type I polyketide synthases (PKS) of the pikromycin pathway in vitro followed by direct appendage of D-desosamine and final C-H oxidation(s) in vivo was developed and applied toward the synthesis of a suite of 12-and 14-membered ring macrolide natural products. This methodology delivered both compound classes in thirteen steps (longest linear sequence) from commercially available (R)-Roche ester in >10% overall yields. PMID:23866020

  17. Highly regio- and diastereoselective, acidic clay supported intramolecular nitrile oxide-alkene cycloaddition on D-ribose derived nitriles: an efficient synthetic route to isoxazoline fused five and six membered carbocycles.

    PubMed

    Panda, Amarendra; Das, Sulagna; Pal, Shantanu

    2014-10-29

    An efficient synthetic route to isoxazoline fused carbocycles from carbohydrate scaffolds that comprise of free hydroxyl group(s) is described with high regio- and stereoselectivity. Montmorillonite K-10/chloramine T oxidation and in situ intramolecular nitrile oxide-alkene cycloaddition (INOC) of D-ribose derived oximes have been developed for the diversity oriented synthesis of isoxazoline fused five and six membered carbocycles. Copyright © 2014 Elsevier Ltd. All rights reserved.

  18. Biocatalytic transformations of hydrothermal fluids

    NASA Astrophysics Data System (ADS)

    Jannasch, H. W.

    The occurrence of copious animal populations at deep-sea vents indicates an effective microbial chemosynthetic biocatalysis of hydrothermal fluids on their emission into oxygenated ambient seawater. The large metabolic and physiological diversity of microbes found at these sites, including anaerobic and aerobic hyperthermophiles, reflects an even higher variety of biocatalytic or enzymatic reactions that greatly influence deep-sea hydrothermal geochemistry.

  19. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    DOE PAGES

    La, Y. S.; Camredon, M.; Ziemann, P. J.; ...

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chambermore » experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.« less

  20. Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: Explicit modeling of SOA formation from alkane and alkene oxidation

    SciTech Connect

    La, Y. S.; Camredon, M.; Ziemann, P. J.; Valorso, R.; Matsunaga, A.; Lannuque, V.; Lee-Taylor, J.; Hodzic, A.; Madronich, S.; Aumont, B.

    2016-02-08

    Recent studies have shown that low volatility gas-phase species can be lost onto the smog chamber wall surfaces. Although this loss of organic vapors to walls could be substantial during experiments, its effect on secondary organic aerosol (SOA) formation has not been well characterized and quantified yet. Here the potential impact of chamber walls on the loss of gaseous organic species and SOA formation has been explored using the Generator for Explicit Chemistry and Kinetics of the Organics in the Atmosphere (GECKO-A) modeling tool, which explicitly represents SOA formation and gas–wall partitioning. The model was compared with 41 smog chamber experiments of SOA formation under OH oxidation of alkane and alkene series (linear, cyclic and C12-branched alkanes and terminal, internal and 2-methyl alkenes with 7 to 17 carbon atoms) under high NOx conditions. Simulated trends match observed trends within and between homologous series. The loss of organic vapors to the chamber walls is found to affect SOA yields as well as the composition of the gas and the particle phases. Simulated distributions of the species in various phases suggest that nitrates, hydroxynitrates and carbonylesters could substantially be lost onto walls. The extent of this process depends on the rate of gas–wall mass transfer, the vapor pressure of the species and the duration of the experiments. Furthermore, this work suggests that SOA yields inferred from chamber experiments could be underestimated up a factor of 2 due to the loss of organic vapors to chamber walls.

  1. Bioorganometallic chemistry: biocatalytic oxidation reactions with biomimetic nad+/nadh co-factors and [cp*rh(bpy)h]+ for selective organic synthesis

    SciTech Connect

    Lutz, Jochen; Hollman, Frank; Ho, The Vinh; Schnyder, Adrian; Fish, Richard H.; Schmid, Andreas

    2004-03-09

    The biocatalytic, regioselective hydroxylation of 2-hydroxybiphenyl to the corresponding catechol was accomplished utilizing the monooxygenase 2-hydroxybiphenyl 3-monooxygenase (HbpA). The necessary natural nicotinamide adenine dinucleotide (NAD{sup +}) co-factor for this biocatalytic process was replaced by a biomimetic co-factor, N-benzylnicotinamide bromide, 1a. The interaction between the flavin (FAD) containing HbpA enzyme and the corresponding biomimetic NADH compound, N-benzyl-1,4-dihdronicotinamide, 1b, for hydride transfers, was shown to readily occur. The in situ recycling of the reduced NADH biomimic 1b from 1a was accomplished with [Cp*Rh(bpy)H](Cl); however, productive coupling of this regeneration reaction to the enzymatic hydroxylation reaction was not totally successful, due to a deactivation process concerning the HbpA enzyme peripheral groups; i.e., -SH or -NH{sub 2} possibly reacting with the precatalyst, [Cp*Rh(bpy)(H{sub 2}O)](Cl){sub 2}, and thus inhibiting the co-factor regeneration process. The deactivation mechanism was studied, and a promising strategy of derivatizing these peripheral -SH or -NH{sub 2} groups with a polymer containing epoxide was successful in circumventing the undesired interaction between HbpA and the precatalyst. This latter strategy allowed tandem co-factor regeneration using 1a or 2a, [Cp*Rh(bpy)(H2O)](Cl){sub 2}, and formate ion, in conjunction with the polymer bound, FAD containing HbpA enzyme to provide the catechol product.

  2. cis-1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers: Os(V)(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand.

    PubMed

    Sugimoto, Hideki; Mikami, Akine; Kai, Kenichiro; Sajith, P K; Shiota, Yoshihito; Yoshizawa, Kazunari; Asano, Kaori; Suzuki, Takeyuki; Itoh, Shinobu

    2015-07-20

    Catalytic activity of [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1: L-N4Me2 = N,N'-dimethyl-2,11-diaza-[3,3](2,6)pyridinophane) in 1,2-cis-aminohydroxylation of alkenes with sodium N-chloro-4-methylbenzenesulfonamide (chloramine-T) is explored. Simple alkenes as well as those containing several types of substituents are converted to the corresponding 1,2-aminoalcohols in modest to high yields. The aminoalcohol products have exclusively cis conformation with respect to the introduced -OH and -NHTs groups. The spectroscopic measurements including cold mass spectroscopic study of the reaction product of complex 1 and chloromine-T as well as density functional theory (DFT) calculations indicate that an oxido-aminato-osmium(V) species [Os(V)(O)(NHTs)(L-N4Me2)](PF6)2 (2) is an active oxidant for the aminohydroxylation. The DFT calculations further indicate that the reaction involves a [3 + 2] cycloaddition between 2 and alkene, and the regioselectivity in the aminohydroxylation of unsymmetrical alkenes is determined by the orientation that bears less steric hindrance from the tosylamino group, which leads to the energetically more preferred product isomer.

  3. Ozonolysis of surface-adsorbed methoxyphenols: kinetics of aromatic ring cleavage vs. alkene side-chain oxidation

    NASA Astrophysics Data System (ADS)

    O'Neill, E. M.; Kawam, A. Z.; Van Ry, D. A.; Hinrichs, R. Z.

    2014-01-01

    Lignin pyrolysis products, which include a variety of substituted methoxyphenols, constitute a major component of organics released by biomass combustion, and may play a central role in the formation of atmospheric brown carbon. Understanding the atmospheric fate of these compounds upon exposure to trace gases is therefore critical to predicting the chemical and physical properties of biomass burning aerosol. We used diffuse reflectance infrared spectroscopy to monitor the heterogeneous ozonolysis of 4-propylguaiacol, eugenol, and isoeugenol adsorbed on NaCl and α-Al2O3 substrates. Adsorption of gaseous methoxyphenols onto these substrates produced near-monolayer surface concentrations of 3 × 1018 molecules m-2. The subsequent dark heterogeneous ozonolysis of adsorbed 4-propylguaiacol cleaved the aromatic ring between the methoxy and phenol groups with the product conclusively identified by GC-MS and 1H-NMR. Kinetic analysis of eugenol and isoeugenol dark ozonolysis also suggested the formation of ring-cleaved products, although ozonolysis of the unsaturated substituent groups forming carboxylic acids and aldehydes was an order of magnitude faster. Average uptake coefficients for NaCl-adsorbed methoxyphenols were γ = 2.3 (± 0.8) × 10-7 and 2 (± 1) × 10-6 for ozonolysis of the aromatic ring and the unsaturated side chain, respectively, and reactions on α-Al2O3 were approximately two times slower. UV-visible radiation (λ > 300 nm) enhanced eugenol ozonolysis of the aromatic ring by a factor of 4(± 1) but had no effect on ozonolysis of the alkene side chain.

  4. Hydroxyl-directed stereoselective diboration of alkenes.

    PubMed

    Blaisdell, Thomas P; Caya, Thomas C; Zhang, Liang; Sanz-Marco, Amparo; Morken, James P

    2014-07-02

    An alkoxide-catalyzed directed diboration of alkenyl alcohols is described. This reaction occurs in a stereoselective fashion and is demonstrated with cyclic and acyclic homoallylic and bishomoallylic alcohol substrates. After oxidation, the reaction generates 1,2-diols such that the process represents a method for the stereoselective directed dihydroxylation of alkenes.

  5. The Biocatalytic Desulfurization Project

    SciTech Connect

    David Nunn; James Boltz; Philip M. DiGrazia; Larry Nace

    2006-03-03

    The material in this report summarizes the Diversa technical effort in development of a biocatalyst for the biodesulfurization of Petro Star diesel as well as an economic report of standalone and combined desulfurization options, prepared by Pelorus and Anvil, to support and inform the development of a commercially viable process. We will discuss goals of the projected as originally stated and their modification as guided by parallel efforts to evaluate commercialization economics and process parameters. We describe efforts to identify novel genes and hosts for the generation of an optimal biocatalyst, analysis of diesel fuels (untreated, chemically oxidized and hydrotreated) for organosulfur compound composition and directed evolution of enzymes central to the biodesulfurization pathway to optimize properties important for their use in a biocatalyst. Finally we will summarize the challenges and issues that are central to successful development of a viable biodesulfurization process.

  6. Unusual aggregates from the oxidation of alkene self-assembled monolayers: a previously unrecognized mechanism for SAM ozonolysis?

    SciTech Connect

    Mcintire, Theresa M.; Lea, Alan S.; Gaspar, Dan J.; Jaitly, Navdeep; Dubowski, Y.; Li, Qiquang; Finlayson-Pitts, Barbara J.

    2005-09-30

    Airborne particles are important in climate, visibility, human health and atmospheric reactions. Organics associated with airborne particles are thought to be oxidized to polar, hygroscopic species with enhanced cloud-nucleating properties. We show that ozone oxidation of unsaturated organics on silica as a proxy for airborne dust leads to the formation of hydrophobic polymer balls which do not increase the uptake of water as previously assumed. We propose that atmospheric formation of hydrophobic polymers is generally controlled by the availability of water rather than acid, and hence is much more common in the lower atmosphere than previously recognized.

  7. The Oxidation of Terminal Alkenes by Permanganate: A Practical Demonstration of the Use of Phase Transfer Agents.

    ERIC Educational Resources Information Center

    Brown, Keith C.; And Others

    1982-01-01

    Use of phase transfer agents to facilitate/accelerate chemical reactions has become an established practice, particularly in organic chemistry. Describes an undergraduate laboratory procedure demonstrating the principles involved in the use of said agents. Includes student results from phase transfer assisted permanganate oxidations. (Author/JN)

  8. THE BIOCATALYTIC DESULFURIZATION PROJECT

    SciTech Connect

    Steven E. Bonde; David Nunn

    2003-04-01

    Research activities in the second quarter have largely been a continuation of efforts previously described in the first quarterly report as well as a degree of redirection of effort as a result of discussions during the first quarterly meeting held in San Diego. Chemical synthesis efforts have been refined and are currently being used to support generation of substrates for evaluation and evolution of enzymes for their oxidation. Analysis of the sulfur species in Petro Star diesel, CED extract and refinement of the speciation data is nearly complete. Molecular biology efforts continue with the cloning, expression and characterization of the DszA and DszC proteins as well as the flavin reductases to support regeneration of the essential FMN cofactors. In addition, we have initiated an evolution effort for the extension and improvement of DszA enzyme activity using Diversa's Gene Site Saturation Mutagenesis (GSSM{trademark}) technology. To support the evolution effort as well as of characterization of enzyme activities on a variety of substrates, a high-throughput mass spectroscopy-based assay has been developed. Two selection/screen strategies for the discovery and evolution of biocatalyst enzyme have been developed and are being evaluated for performance using gene libraries constructed from known biodesulfurization strains and environmental libraries.

  9. THE BIOCATALYTIC DESULFURIZATION PROJECT

    SciTech Connect

    Steven E. Bonde; David Nunn

    2003-01-01

    During the first quarter of the Biological Desulfurization project several activities were pursued. A project kickoff meeting was held at the Diversa facility in San Diego, CA. Activities that were in process before the meeting and begun afterwards by Diversa Corporation and Petro Star Inc. include: Technology transfer in the form of information generated by Enchira to Diversa, the purchase and installation of equipment by Diversa, development of synthetic methods and preparation of organo-sulfur substrates for use in determining enzyme activities, production of extract via Petro Star's CED process, detailed analysis of Petro Star Inc. diesel and CED extract, and several activities in molecular biology. Diversa Corporation, in the area of molecular biology, engaged in several activities in support of the task list of the contract. These included: construction of a genomic library; development and utilization of a sequence-based gene discovery effort; a parallel discovery approach based on functional expression of enzymes with the ability to oxidize organosulfur compounds. Biodesulfurization genes have already been identified and are being sequenced and subcloned for expression in heterologous biological hosts. Diversa has evaluated and adapted assays developed by Enchira used to assess the activities of DBT and DBTO{sub 2} monooxygenases. Finally, Diversa personnel have developed two novel selection/screen strategies for the improvement of biocatalyst strains by directed evolution.

  10. Synthesis and Application of Chiral Spiro Cp Ligands in Rhodium-Catalyzed Asymmetric Oxidative Coupling of Biaryl Compounds with Alkenes.

    PubMed

    Zheng, Jun; Cui, Wen-Jun; Zheng, Chao; You, Shu-Li

    2016-04-27

    The vastly increasing application of chiral Cp ligands in asymmetric catalysis results in growing demand for novel chiral Cp ligands. Herein, we report a new class of chiral Cp ligands based on 1,1'-spirobiindane, a privileged scaffold for chiral ligands and catalysts. The corresponding Rh complexes are shown to be excellent catalysts in asymmetric oxidative coupling reactions, providing axially chiral biaryls in 19-97% yields with up to 98:2 er.

  11. Reversible Alkene Insertion into the Pd–N Bond of Pd(II)-Sulfonamidates and Implications for Catalytic Amidation Reactions

    PubMed Central

    White, Paul B.; Stahl, Shannon S.

    2011-01-01

    Alkene insertion into Pd–N bonds is a key step in Pd-catalyzed oxidative amidation of alkenes. A series of well-defined Pd(II)-sulfonamidate complexes have been prepared and shown to react via insertion of a tethered alkene. The Pd–amidate and resulting Pd–alkyl species have been crystallographically characterized. The alkene insertion reaction is found to be reversible, but complete conversion to oxidative amination products is observed in the presence of O2. Electronic-effect studies reveal that alkene insertion into the Pd–N bond is favored kinetically and thermodynamically with electron-rich amidates. PMID:22007610

  12. Reversible alkene insertion into the Pd-N bond of Pd(II)-sulfonamidates and implications for catalytic amidation reactions.

    PubMed

    White, Paul B; Stahl, Shannon S

    2011-11-23

    Alkene insertion into Pd-N bonds is a key step in Pd-catalyzed oxidative amidation of alkenes. A series of well-defined Pd(II)-sulfonamidate complexes have been prepared and shown to react via insertion of a tethered alkene. The Pd-amidate and resulting Pd-alkyl species have been crystallographically characterized. The alkene insertion reaction is found to be reversible, but complete conversion to oxidative amination products is observed in the presence of O(2). Electronic-effect studies reveal that alkene insertion into the Pd-N bond is favored kinetically and thermodynamically with electron-rich amidates.

  13. Biocatalytic conversion of lignocellulose to platform chemicals.

    PubMed

    Jäger, Gernot; Büchs, Jochen

    2012-09-01

    Naturally occurring lignocellulose can be used as a renewable resource for the sustainable production of platform chemicals that can in turn be converted to valuable fine chemicals, polymers, and fuels. The biocatalytic conversion of lignocellulose is a very promising approach due to its high selectivity, mild conditions, and low exergy loss. However, such biocatalytic processes are still seldom applied at the industrial scale since the single conversion steps (pretreatment, hydrolysis, and fermentation) may exhibit low conversion rates, low efficiencies, or high costs. The biocatalytic conversion of lignocellulose to platform chemicals is reviewed in this work. Structures and production rates of lignocellulose are described, and platform chemicals that may be produced from lignocellulose are summarized. Biocatalytic conversion of lignocellulose is distinguished from conventional non-selective approaches. All essential conversion steps used in biocatalytic approaches (pretreatment, hydrolysis, and fermentation) are reviewed in detail. Finally, potential interactions between these conversion steps are highlighted and the advantages as well as disadvantages of integrated process configurations are elucidated. In conclusion, a comprehensive understanding of the biocatalytic conversion of lignocellulose is provided in this review.

  14. Methods of producing epoxides from alkenes using a two-component catalyst system

    SciTech Connect

    Kung, Mayfair C.; Kung, Harold H.; Jiang, Jian

    2013-07-09

    Methods for the epoxidation of alkenes are provided. The methods include the steps of exposing the alkene to a two-component catalyst system in an aqueous solution in the presence of carbon monoxide and molecular oxygen under conditions in which the alkene is epoxidized. The two-component catalyst system comprises a first catalyst that generates peroxides or peroxy intermediates during oxidation of CO with molecular oxygen and a second catalyst that catalyzes the epoxidation of the alkene using the peroxides or peroxy intermediates. A catalyst system composed of particles of suspended gold and titanium silicalite is one example of a suitable two-component catalyst system.

  15. Biocatalytic Conversion of Avermectin to 4"-Oxo-Avermectin: Characterization of Biocatalytically Active Bacterial Strains and of Cytochrome P450 Monooxygenase Enzymes and Their Genes

    PubMed Central

    Jungmann, Volker; Molnár, István; Hammer, Philip E.; Hill, D. Steven; Zirkle, Ross; Buckel, Thomas G.; Buckel, Dagmar; Ligon, James M.; Pachlatko, J. Paul

    2005-01-01

    4"-Oxo-avermectin is a key intermediate in the manufacture of the agriculturally important insecticide emamectin benzoate from the natural product avermectin. Seventeen biocatalytically active Streptomyces strains with the ability to oxidize avermectin to 4"-oxo-avermectin in a regioselective manner have been discovered in a screen of 3,334 microorganisms. The enzymes responsible for this oxidation reaction in these biocatalytically active strains were found to be cytochrome P450 monooxygenases (CYPs) and were termed Ema1 to Ema17. The genes for Ema1 to Ema17 have been cloned, sequenced, and compared to reveal a new subfamily of CYPs. Ema1 to Ema16 have been overexpressed in Escherichia coli and purified as His-tagged recombinant proteins, and their basic enzyme kinetic parameters have been determined. PMID:16269732

  16. Catalytic, Stereospecific Syn-Dichlorination of Alkenes

    PubMed Central

    Cresswell, Alexander J.; Eey, Stanley T.-C.; Denmark, Scott E.

    2015-01-01

    As some of the oldest organic chemical reactions known, the ionic additions of elemental halogens such as bromine and chlorine to alkenes are prototypical examples of stereospecific reactions, typically delivering vicinal dihalides resulting from anti-addition. Whilst the invention of enantioselective variants is an ongoing challenge, the ability to overturn the intrinsic anti-diastereospecificity of these transformations is also a largely unsolved problem. In this Article, we describe the first catalytic, syn-stereospecific dichlorination of alkenes, employing a group transfer catalyst based on a redox-active main group element (i.e., selenium). Thus, with diphenyl diselenide (PhSeSePh) (5 mol %) as the pre-catalyst, benzyltriethylammonium chloride (BnEt3NCl) as the chloride source, and an N-fluoropyridinium salt as the oxidant, a wide variety of functionalized cyclic and acyclic 1,2-disubstituted alkenes, including simple allylic alcohols, deliver syn-dichlorides with exquisite stereocontrol. This methodology is expected to find applications in streamlining the synthesis of polychlorinated natural products such as the chlorosulfolipids. PMID:25615668

  17. Engineering the biocatalytic selectivity of iridoid production in Saccharomyces cerevisiae.

    PubMed

    Billingsley, John M; DeNicola, Anthony B; Barber, Joyann S; Tang, Man-Cheng; Horecka, Joe; Chu, Angela; Garg, Neil K; Tang, Yi

    2017-09-20

    Monoterpene indole alkaloids (MIAs) represent a structurally diverse, medicinally essential class of plant derived natural products. The universal MIA building block strictosidine was recently produced in the yeast Saccharomyces cerevisiae, setting the stage for optimization of microbial production. However, the irreversible reduction of pathway intermediates by yeast enzymes results in a non-recoverable loss of carbon, which has a strong negative impact on metabolic flux. In this study, we identified and engineered the determinants of biocatalytic selectivity which control flux towards the iridoid scaffold from which all MIAs are derived. Development of a bioconversion based production platform enabled analysis of the metabolic flux and interference around two critical steps in generating the iridoid scaffold: oxidation of 8-hydroxygeraniol to the dialdehyde 8-oxogeranial followed by reductive cyclization to form nepetalactol. In vitro reconstitution of previously uncharacterized shunt pathways enabled the identification of two distinct routes to a reduced shunt product including endogenous 'ene'-reduction and non-productive reduction by iridoid synthase when interfaced with endogenous alcohol dehydrogenases. Deletion of five genes involved in α,β-unsaturated carbonyl metabolism resulted in a 5.2-fold increase in biocatalytic selectivity of the desired iridoid over reduced shunt product. We anticipate that our engineering strategies will play an important role in the development of S. cerevisiae for sustainable production of iridoids and MIAs. Copyright © 2017 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

  18. Biocatalytic Processing Polymers in Supercritical Fluids

    DTIC Science & Technology

    1994-01-01

    Russell, A.J and Beckman, E.J. (1991) Appl. Bioch . Biotech., 31, 197-211. Enzyme activity in supercritical fluids. 22. *Russell, A.J and Beckman, E.J...S., Jacob , J., Beckman, E.J. and Russell, A.J. (1991) Enz. Microb. Technol., 13, 519. Biocatalytic synthesis of acrylates in supercritical fluids. 24

  19. Microanalysis of Alkenes by Ozonolysis

    ERIC Educational Resources Information Center

    Luibrand, R. T.; Vollmer, J. J.

    1975-01-01

    Describes an undergraduate laboratory experiment in which the position of the double bond in an alkene is determined by identifying its ozonolysis products. This experiment can also be used to introduce the technique of gas chromatography. (MLH)

  20. Microanalysis of Alkenes by Ozonolysis

    ERIC Educational Resources Information Center

    Luibrand, R. T.; Vollmer, J. J.

    1975-01-01

    Describes an undergraduate laboratory experiment in which the position of the double bond in an alkene is determined by identifying its ozonolysis products. This experiment can also be used to introduce the technique of gas chromatography. (MLH)

  1. Pyridine is an organocatalyst for the reductive ozonolysis of alkenes

    PubMed Central

    Willand-Charnley, Rachel; Fisher, Thomas J.; Johnson, Bradley M.; Dussault, Patrick H.

    2012-01-01

    Whereas the cleavage of alkenes by ozone typically generates peroxide intermediates that must be decomposed in an accompanying step, ozonolysis in the presence of pyridine directly generates ketones or aldehydes through a process that neither consumes pyridine nor generates any detectable peroxides. The reaction is hypothesized to involve nucleophile-promoted fragmentation of carbonyl oxides via formation of zwitterionic peroxyacetals. PMID:22512349

  2. The Industrial Age of Biocatalytic Transamination

    PubMed Central

    Fuchs, Michael; Farnberger, Judith E; Kroutil, Wolfgang

    2015-01-01

    During the last decade the use of ω-transaminases has been identified as a very powerful method for the preparation of optically pure amines from the corresponding ketones. Their immense potential for the preparation of chiral amines, together with their ease of use in combination with existing biocatalytic methods, have made these biocatalysts a competitor to any chemical methodology for (asymmetric) amination. An increasing number of examples, especially from industry, shows that this biocatalytic technology outmaneuvers existing chemical processes by its simple and flexible nature. In the last few years numerous publications and patents on synthetic routes, mainly to pharmaceuticals, involving ω-transaminases have been published. The review gives an overview of the application of ω-transaminases in organic synthesis with a focus on active pharmaceutical ingredients (APIs) and the developments during the last few years. PMID:26726292

  3. Efficient Biocatalytic Synthesis of Chiral Chemicals.

    PubMed

    Zhang, Zhi-Jun; Pan, Jiang; Ma, Bao-Di; Xu, Jian-He

    2016-01-01

    Chiral chemicals are a group of important chiral synthons for the synthesis of a series of pharmaceuticals, agrochemicals, and fine chemicals. In past decades, a number of biocatalytic approaches have been developed for the green and effective synthesis of various chiral chemicals. However, the practical application of these biocatalytic processes is still hindered by the lack of highly efficient and robust biocatalysts, which usually results in the low volumetric productivity and high cost of the bioprocesses. Further step forward of biocatalysis in industrial application strongly requires the development of versatile and highly efficient biocatalysts, aiming to increase the process efficiency and facilitate the downstream processing. Recently, the fast growth of genome sequences in the database in post-genomic era offers great opportunities for accessing numerous biocatalysts with practical application potential, and the so-called genome mining approach provides time-effective and highly specific strategy for the fast identification of target enzymes with desired properties and outperforms the traditional screening of soil samples for microbial enzyme producers of interest. A number of biocatalytic processes with industrial application potential were developed thereafter. Further development of protein engineering strategies, process optimization, and cooperative work between biologists, organic chemists, and engineers is expected to make biocatalysis technology the first choice approach for the eco-friendly, highly efficient, and cost-effective synthesis of chiral chemicals in the near future.

  4. Biogenic Emissions of Light Alkenes from a Coniferous Forest

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Turnipseed, A. A.; Martinez, L.; Shen, S.; De Gouw, J. A.; Warneke, C.; Koss, A.; Lerner, B. M.; Miller, B. R.; Smith, J. N.; Guenther, A. B.

    2014-12-01

    Alkenes are reactive hydrocarbons that play important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The light alkenes (C2-C4) originate from both biogenic and anthropogenic sources and include C2H4 (ethene), C3H6 (propene) and C4H8 (1-butene, 2-butene, 2-methylpropene). Light alkenes are used widely as chemical feedstocks because their double bond makes them versatile for industrial reactions. Their biogenic sources are poorly characterized, with most global emissions estimates relying on laboratory-based studies; net ecosystem emissions have been measured at only one site thus far. Here we report net ecosystem fluxes of light alkenes and isoprene from a semi-arid ponderosa pine forest in the Rocky Mountains of Colorado, USA. Canopy scale fluxes were measured using relaxed eddy accumulation (REA) techniques on the 28-meter NCAR tower in the Manitou Experimental Forest Observatory. Updrafts and downdrafts were determined by sonic anemometry and segregated into 'up' and 'down' reservoirs over the course of an hour. Samples were then measured on two separate automated gas chromatographs (GCs). The first GC measured light hydrocarbons (C2-C6 alkanes and C2-C5 alkenes) by flame ionization detection (FID). The second GC measured halocarbons (methyl chloride, CFC-12, and HCFC-22) by electron capture detection (ECD). Additional air measurements from the top of the tower included hydrocarbons and their oxidation products by Proton Transfer Reaction Mass Spectrometry (PTR-MS). Three field intensives were conducted during the summer of 2014. The REA flux measurements showed that ethene, propene and the butene emissions have significant diurnal cycles, with maximum emissions at midday. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons and have a temporal variability that may be associated with physical and biological parameters. These ecosystem scale measurements

  5. An ene reductase from Clavispora lusitaniae for asymmetric reduction of activated alkenes.

    PubMed

    Ni, Yan; Yu, Hui-Lei; Lin, Guo-Qiang; Xu, Jian-He

    2014-03-05

    A putative ene reductase gene from Clavispora lusitaniae was heterologously overexpressed in Escherichia coli, and the encoded protein (ClER) was purified and characterized for its biocatalytic properties. This NADPH-dependent flavoprotein was identified with reduction activities toward a diverse range of activated alkenes including conjugated enones, enals, maleimide derivative and α,β-unsaturated carboxylic esters. The purified ClER exhibited a relatively high activity of 7.3 U mg(prot)⁻¹ for ketoisophorone while a remarkable catalytic efficiency (k(cat)/K(m)=810 s⁻¹ mM⁻¹) was obtained for 2-methyl-cinnamaldehyde due to the high affinity. A series of prochiral activated alkenes were stereoselectively reduced by ClER furnishing the corresponding saturated products in up to 99% ee. The practical applicability of ClER was further evaluated for the production of (R)-levodione, a valuable chiral compound, from ketoisophorone. Using the crude enzyme of ClER and glucose dehydrogenase (GDH), 500 mM of ketoisophorone was efficiently converted to (R)-levodione with excellent stereoselectivity (98% ee) within 1h. All these positive features demonstrate a high synthetic potential of ClER in the asymmetric reduction of activated alkenes.

  6. The arene–alkene photocycloaddition

    PubMed Central

    Streit, Ursula

    2011-01-01

    Summary In the presence of an alkene, three different modes of photocycloaddition with benzene derivatives can occur; the [2 + 2] or ortho, the [3 + 2] or meta, and the [4 + 2] or para photocycloaddition. This short review aims to demonstrate the synthetic power of these photocycloadditions. PMID:21647263

  7. Mixed regiospecificity compromises alkene synthesis by a cytochrome P450 peroxygenase from Methylobacterium populi.

    PubMed

    Amaya, Jose A; Rutland, Cooper D; Makris, Thomas M

    2016-05-01

    Intensive interest has focused on enzymes that are capable of synthesizing hydrocarbons, alkenes and alkanes, for sustainable fuel production. A recently described cytochrome P450 (OleTJE) from the CYP152 family catalyzes an unusual carbon-carbon scission reaction, transforming Cn fatty acids to Cn-1 1-alkenes. Here, we show that a second CYP152, CYP-MP from Methylobacterium populi ATCC BAA 705, also catalyzes oxidative substrate decarboxylation. Alkene production is accompanied with the production of fatty alcohol products, underscoring the mechanistic similarity of the decarboxylation reaction with canonical P450 monooxygenation chemistry. The branchpoint of these two chemistries, and regiospecificity of oxidation products, is strongly chain length dependent, suggesting an importance of substrate coordination for regulating alkene production. Copyright © 2016 Elsevier Inc. All rights reserved.

  8. Rhodium-catalysed syn-carboamination of alkenes via a transient directing group.

    PubMed

    Piou, Tiffany; Rovis, Tomislav

    2015-11-05

    Alkenes are the most ubiquitous prochiral functional groups--those that can be converted from achiral to chiral in a single step--that are accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes (whereby two functional groups are added to the same double bond) are particularly important, as they can be used to produce highly complex molecular architectures. Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation, are well established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. Here we describe the rhodium-catalysed carboamination of alkenes at the same (syn) face of a double bond, initiated by a carbon-hydrogen activation event that uses enoxyphthalimides as the source of both the carbon and the nitrogen functionalities. The reaction methodology allows for the intermolecular, stereospecific formation of one carbon-carbon and one carbon-nitrogen bond across an alkene, which is, to our knowledge, unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a new cyclopentadienyl ligand to control the reactivity of rhodium. The results provide a new way of synthesizing functionalized alkenes, and should lead to the convergent and stereoselective assembly of amine-containing acyclic molecules.

  9. Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group

    PubMed Central

    Piou, Tiffany; Rovis, Tomislav

    2015-01-01

    Alkenes are the most ubiquitous pro-chiral functional groups accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes are particularly important, as they can be used to access highly complex molecular architectures.1,2 Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation reactions,3,4,5,6 are well-established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. In this manuscript, we describe the Rh(III)-catalyzed syn carboamination of alkenes initiated by a C–H activation event that uses enoxyphthalimides as the source of the carbon and the nitrogen functionalities. The reaction methodology allows for the stereospecific formation of one C–C and one C–N bond across an alkene in a fully intermolecular sense, which is unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a novel cyclopentadienyl ligand to control the reactivity of Rh(III). The results provide a new route to functionalized alkenes and are expected to lead to the more convergent and stereoselective assembly of amine-containing acyclic molecules. PMID:26503048

  10. Observation of a ferric hydroperoxide complex during the non-heme iron catalysed oxidation of alkenes and alkanes by O2.

    PubMed

    He, Yu; Goldsmith, Christian R

    2012-11-04

    A non-heme iron complex catalyses the oxidation of allylic, benzylic, and aliphatic C-H bonds by O(2). During this reactivity, a ferric hydroperoxide species is observed. The kinetic analysis of this complex's formation may suggest a ferric superoxo species as the initial metal-based oxidant.

  11. Alkene Metalates as Hydrogenation Catalysts.

    PubMed

    Büschelberger, Philipp; Gärtner, Dominik; Reyes-Rodriguez, Efrain; Kreyenschmidt, Friedrich; Koszinowski, Konrad; Jacobi von Wangelin, Axel; Wolf, Robert

    2017-03-02

    First-row transition-metal complexes hold great potential as catalysts for hydrogenations and related reductive reactions. Homo- and heteroleptic arene/alkene metalates(1-) (M=Co, Fe) are a structurally distinct catalyst class with good activities in hydrogenations of alkenes and alkynes. The first syntheses of the heteroleptic cobaltates [K([18]crown-6)][Co(η(4) -cod)(η(2) -styrene)2 ] (5) and [K([18]crown-6)][Co(η(4) -dct)(η(4) -cod)] (6), and the homoleptic complex [K(thf)2 ][Co(η(4) -dct)2 ] (7; dct=dibenzo[a,e]cyclooctatetraene, cod=1,5-cyclooctadiene), are reported. For comparison, two cyclopentadienylferrates(1-) were synthesized according to literature procedures. The isolated and fully characterized monoanionic complexes were competent precatalysts in alkene hydrogenations under mild conditions (2 bar H2 , r.t., THF). Mechanistic studies by NMR spectroscopy, ESI mass spectrometry, and poisoning experiments documented the operation of a homogeneous mechanism, which was initiated by facile redox-neutral π-ligand exchange with the substrates followed by H2 activation. The substrate scope of the investigated precatalysts was also extended to polar substrates (ketones and imines).

  12. Biocatalytic spectrophotometric method to detect paracetamol in water samples.

    PubMed

    Méndez-Albores, Alia; Tarín, Cristina; Rebollar-Pérez, Georgette; Dominguez-Ramirez, Lenin; Torres, Eduardo

    2015-01-01

    A biocatalytic methodology based on the quantification of the laccase inhibition during the oxidation of a standard substrate ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) for the indirect determination of paracetamol in drinking water has been developed. The method displayed a fast response time (20 s), and high selectivity to paracetamol in presence of interfering substances such as naproxen, estradiol, ketoprofen, sulfamethoxazole, and diclofenac. The limit of detection (LOD) and limit of quantification (LOQ) were noticed to be 0.55 µM and 8.3 µM, respectively. By comparing the catalytic constants value KM and kcat for ABTS oxidation in the absence and presence of various concentrations of paracetamol, a competitive-type inhibition was disclosed. On the other hand, the close value between Ki and KM indicates similar binding affinity of the enzyme to ABTS and paracetamol corroborated by docking studies. The methodology was successfully applied to real water samples, presenting an interesting potential for further development of a biosensor to paracetamol detection.

  13. Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes.

    PubMed

    Coombs, John R; Morken, James P

    2016-02-18

    Terminal alkenes are readily available functional groups which appear in α-olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1-alkenes is high enough to be useful for asymmetric synthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Palladium-catalyzed stereoselective intramolecular oxidative amidation of alkenes in the synthesis of 1,3- and 1,4-amino alcohols and 1,3-diamines.

    PubMed

    Malkov, Andrei V; Lee, Darren S; Barłóg, Maciej; Elsegood, Mark R J; Kočovský, Pavel

    2014-04-22

    An efficient and practical Pd-catalyzed intramolecular oxidative allylic amidation provides facile access to derivatives of 1,3- and 1,4-amino alcohols and 1,3-diamines. The method operates under mild reaction conditions (RT) with molecular oxygen (1 atm) as the sole reoxidant of Pd. Excellent diastereoselectivities were attained with substrates bearing a secondary stereogenic center.

  15. General catalyst control of the monoisomerization of 1-alkenes to trans-2-alkenes.

    PubMed

    Larsen, Casey R; Erdogan, Gulin; Grotjahn, Douglas B

    2014-01-29

    After searching for the proper catalyst, the dual challenges of controlling the position of the double bond, and cis/trans-selectivity in isomerization of terminal alkenes to their 2-isomers are finally met in a general sense by mixtures of (C5Me5)Ru complexes 1 and 3 featuring a bifunctional phosphine. Typically, catalyst loadings of 1 mol % of 1 and 3 can be employed for the production of (E)-2-alkenes at 40-70 °C. Catalyst comprising 1 and 3 avoids more than any other known example the thermodynamic equilibration of alkene isomers, as the trans-2-alkenes of both nonfunctionalized and functionalized alkenes are generated.

  16. A simple and effective catalytic system for epoxidation of aliphatic terminal alkenes with manganese(II) as the catalyst.

    PubMed

    Ho, Kam-Piu; Wong, Wing-Leung; Lam, Kin-Ming; Lai, Cheuk-Piu; Chan, Tak Hang; Wong, Kwok-Yin

    2008-01-01

    A simple catalytic system that uses commercially available manganese(II) perchlorate as the catalyst and peracetic acid as the oxidant is found to be very effective in the epoxidation of aliphatic terminal alkenes with high product selectivity at ambient temperature. Many terminal alkenes are epoxidised efficiently on a gram scale in less than an hour to give excellent yields of isolated product (>90 %) of epoxides in high purity. Kinetic studies with some C9-alkenes show that the catalytic system is more efficient in epoxidising terminal alkenes than internal alkenes, which is contrary to most commonly known epoxidation systems. The reaction rate for epoxidation decreases in the order: 1-nonene>cis-3-nonene>trans-3-nonene. ESI-MS and EPR spectroscopic studies suggest that the active form of the catalyst is a high-valent oligonuclear manganese species, which probably functions as the oxygen atom-transfer agent in the epoxidation reaction.

  17. Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes - deduced from structure-product relationships

    NASA Astrophysics Data System (ADS)

    Mentel, T. F.; Springer, M.; Ehn, M.; Kleist, E.; Pullinen, I.; Kurtén, T.; Rissanen, M.; Wahner, A.; Wildt, J.

    2015-06-01

    It has been postulated that secondary organic particulate matter plays a pivotal role in the early growth of newly formed particles in forest areas. The recently detected class of extremely low volatile organic compounds (ELVOC) provides the missing organic vapors and possibly contributes a significant fraction to atmospheric SOA (secondary organic aerosol). The sequential rearrangement of peroxy radicals and subsequent O2 addition results in ELVOC which are highly oxidized multifunctional molecules (HOM). Key for efficiency of such HOM in early particle growth is that their formation is induced by one attack of the oxidant (here O3), followed by an autoxidation process involving molecular oxygen. Similar mechanisms were recently observed and predicted by quantum mechanical calculations e.g., for isoprene. To assess the atmospheric importance and therewith the potential generality, it is crucial to understand the formation pathway of HOM. To elucidate the formation path of HOM as well as necessary and sufficient structural prerequisites of their formation we studied homologous series of cycloalkenes in comparison to two monoterpenes. We were able to directly observe highly oxidized multifunctional peroxy radicals with 8 or 10 O atoms by an Atmospheric Pressure interface High Resolution Time of Flight Mass Spectrometer (APi-TOF-MS) equipped with a NO3--chemical ionization (CI) source. In the case of O3 acting as an oxidant, the starting peroxy radical is formed on the so-called vinylhydroperoxide path. HOM peroxy radicals and their termination reactions with other peroxy radicals, including dimerization, allowed for analyzing the observed mass spectra and narrowing down the likely formation path. As consequence, we propose that HOM are multifunctional percarboxylic acids, with carbonyl, hydroperoxy, or hydroxy groups arising from the termination steps. We figured that aldehyde groups facilitate the initial rearrangement steps. In simple molecules like cycloalkenes

  18. Formation of highly oxidized multifunctional compounds: autoxidation of peroxy radicals formed in the ozonolysis of alkenes - deduced from structure-product relationships

    NASA Astrophysics Data System (ADS)

    Mentel, T. F.; Springer, M.; Ehn, M.; Kleist, E.; Pullinen, I.; Kurtén, T.; Rissanen, M.; Wahner, A.; Wildt, J.

    2015-01-01

    It has been postulated that secondary organic particulate matter plays a pivotal role in the early growth of newly formed particles in forest areas. The recently detected class of extremely low volatile organic compounds (ELVOC) provides the missing organic vapours and possibly contributes a~significant fraction to atmospheric SOA. ELVOC are highly oxidized multifunctional molecules (HOM), formed by sequential rearrangement of peroxy radicals and subsequent O2 addition. Key for efficiency in early particle growth is that formation of HOM is induced by one attack of the oxidant (here O3) and followed by an autoxidation process involving molecular oxygen. Similar mechanisms were recently observed and predicted by quantum mechanical calculations e.g. for isoprene. To assess the atmospheric importance and therewith the potential generality, it is crucial to understand the formation pathway of HOM. To elucidate the formation path of HOM as well as necessary and sufficient structural prerequisites of their formation we studied homologues series of cycloalkenes in comparison to two monoterpenes. We were able to directly observe highly oxidized multifunctional peroxy radicals with 8 or 10 O-atoms by an Atmospheric Pressure interface High Resolution Time of Flight Mass Spectrometer equipped with a NO3--Chemical Ionization (CI) source. In case of O3 acting as oxidant the starting peroxy radical is formed on the so called vinylhydroperoxide path. HOM peroxy radicals and their termination reactions with other peroxy radicals, including dimerization, allowed for analysing the observed mass spectra and narrow down the likely formation path. As consequence we propose that HOM are multifunctional percarboxylic acids; with carbonyl-, hydroperoxy-, or hydroxy-groups arising from the termination steps. We figured that aldehyde groups facilitate the initial rearrangement steps. In simple molecules like cyloalkenes autoxidation was limited to both terminal C-atoms and two further C

  19. Systematic methodology for the development of biocatalytic hydrogen-borrowing cascades: application to the synthesis of chiral α-substituted carboxylic acids from α-substituted α,β-unsaturated aldehydes.

    PubMed

    Knaus, Tanja; Mutti, Francesco G; Humphreys, Luke D; Turner, Nicholas J; Scrutton, Nigel S

    2015-01-07

    Ene-reductases (ERs) are flavin dependent enzymes that catalyze the asymmetric reduction of activated carbon-carbon double bonds. In particular, α,β-unsaturated carbonyl compounds (e.g. enals and enones) as well as nitroalkenes are rapidly reduced. Conversely, α,β-unsaturated esters are poorly accepted substrates whereas free carboxylic acids are not converted at all. The only exceptions are α,β-unsaturated diacids, diesters as well as esters bearing an electron-withdrawing group in α- or β-position. Here, we present an alternative approach that has a general applicability for directly obtaining diverse chiral α-substituted carboxylic acids. This approach combines two enzyme classes, namely ERs and aldehyde dehydrogenases (Ald-DHs), in a concurrent reductive-oxidative biocatalytic cascade. This strategy has several advantages as the starting material is an α-substituted α,β-unsaturated aldehyde, a class of compounds extremely reactive for the reduction of the alkene moiety. Furthermore no external hydride source from a sacrificial substrate (e.g. glucose, formate) is required since the hydride for the first reductive step is liberated in the second oxidative step. Such a process is defined as a hydrogen-borrowing cascade. This methodology has wide applicability as it was successfully applied to the synthesis of chiral substituted hydrocinnamic acids, aliphatic acids, heterocycles and even acetylated amino acids with elevated yield, chemo- and stereo-selectivity. A systematic methodology for optimizing the hydrogen-borrowing two-enzyme synthesis of α-chiral substituted carboxylic acids was developed. This systematic methodology has general applicability for the development of diverse hydrogen-borrowing processes that possess the highest atom efficiency and the lowest environmental impact.

  20. Intermolecular cope-type hydroamination of alkenes and alkynes using hydroxylamines.

    PubMed

    Moran, Joseph; Gorelsky, Serge I; Dimitrijevic, Elena; Lebrun, Marie-Eve; Bédard, Anne-Catherine; Séguin, Catherine; Beauchemin, André M

    2008-12-31

    The development of the Cope-type hydroamination as a method for the metal- and acid-free intermolecular hydroamination of hydroxylamines with alkenes and alkynes is described. Aqueous hydroxylamine reacts efficiently with alkynes in a Markovnikov fashion to give oximes and with strained alkenes to give N-alkylhydroxylamines, while unstrained alkenes are more challenging. N-Alkylhydroxylamines also display similar reactivity with strained alkenes and give modest to good yields with vinylarenes. Electron-rich vinylarenes lead to branched products while electron-deficient vinylarenes give linear products. A beneficial additive effect is observed with sodium cyanoborohydride, the extent of which is dependent on the structure of the hydroxylamine. The reaction conditions are found to be compatible with common protecting groups, free OH and NH bonds, as well as bromoarenes. Both experimental and theoretical results suggest the proton transfer step of the N-oxide intermediate is of vital importance in the intermolecular reactions of alkenes. Details are disclosed concerning optimization, reaction scope, limitations, and theoretical analysis by DFT, which includes a detailed molecular orbital description for the concerted hydroamination process and an exhaustive set of calculated potential energy surfaces for the reactions of various alkenes, alkynes, and hydroxylamines.

  1. Group 11 Metal Compounds with Tripodal Bis(imidazole) Thioether Ligands. Applications as Catalysts in the Oxidation of Alkenes and as Antimicrobial Agents

    PubMed Central

    Liu, Fangwei; Anis, Reema; Hwang, Eunmi; Ovalle, Rafael; Varela-Ramírez, Armando; Aguilera, Renato J.; Contel, María

    2011-01-01

    New group 11 metal complexes have been prepared using the previously described tripodal bis(imidazole) thioether ligand (N-methyl-4,5-diphenyl-2-imidazolyl)2C(OMe)C(CH3)2S(tert-Bu) ({BITOMe,StBu}, 2). The pincer ligand offers a N2S donor atom set that can be used to coordinate the group 11 metals in different oxidation states [AuI, AuIII, AgI, CuI and CuII]. Thus the new compounds [Au{BITOMe,StBu}Cl][AuCl4]2 (3), [Au{BITOMe,StBu}Cl] (4), [Ag{BITOMe,StBu}X] (X = OSO2CF3 − 5, PF6 − 6) and [Cu{BITOMe,StBu}Cl2] (7) have been synthesized from reaction of 2 with the appropriate metal precursors, and characterized in solution. While attempting characterization in the solid state of 3, single crystals of the neutral dinuclear mixed AuIII-AuI species [Au2{BITOMe,S}Cl3] (8) were obtained and its crystal structure was determined by X-ray diffraction studies. The structure shows a AuIII center coordinated to the pincer ligand through one N and the S atom. The soft AuI center coordinates to the ligand through the same S atom that has lost the tert-butyl group, thus becoming a thiolate ligand. The short distance between the AuI–AuIII atoms (3.383 Å) may indicate a weak metal-metal interaction. Complexes 2–7 and the previously described CuI compound [Cu{BITOMe,StBu}]PF6 (9) have been evaluated in the oxidation of biphenyl ethylene with tert-butyl hydrogen peroxide (TBHP) as the oxidant. Results have shown that the AuI and AgI complexes 4 and 6 (at 10 mol % loading) are the more active catalysts in this oxidative cleavage. The antimicrobial activity of compounds 2–5, 7 and 9 against Gram-positive and Gram-negative bacteria and yeast has also been evaluated. The new gold and silver compounds display moderate to high antibacterial activity, while the copper derivatives are mostly inactive. The gold and silver complexes were also potent against fungi. Their cytotoxic properties have been analyzed in vitro utilizing HeLa human cervical carcinoma cells. The compounds

  2. Carbonylations of alkenes with CO surrogates.

    PubMed

    Wu, Lipeng; Liu, Qiang; Jackstell, Ralf; Beller, Matthias

    2014-06-16

    Alkene carbonylation reactions are important for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. In fact, these properties impede the wider use of carbonylation reactions in industry and academia. Hence, performing carbonylations without the use of CO is highly desired and will contribute to the further advancement of sustainable chemistry. Although the use of carbon monoxide surrogates in alkene carbonylation reactions has been reported intermittently in the last 30 years, only recently has this area attracted significant interest. This Minireview summarizes carbonylation reactions of alkenes using different carbon monoxide surrogates.

  3. Alkene syn dihydroxylation with malonoyl peroxides.

    PubMed

    Griffith, James C; Jones, Kevin M; Picon, Sylvain; Rawling, Michael J; Kariuki, Benson M; Campbell, Matthew; Tomkinson, Nicholas C O

    2010-10-20

    Cyclopropyl malonoyl peroxide (1), which can be prepared in a single step from the commercially available diacid, is an effective reagent for the dihydroxylation of alkenes. Reaction of 1 with an alkene in the presence of 1 equiv of water at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (40-93%). With 1,2-disubstituted alkenes, the reaction proceeds with syn selectivity (3:1 to >50:1). A mechanism consistent with the experimental findings that is supported by oxygen-labeling studies is proposed.

  4. Remote functionalization through alkene isomerization.

    PubMed

    Vasseur, Alexandre; Bruffaerts, Jeffrey; Marek, Ilan

    2016-03-01

    Exploiting the reactivity of one functional group within a molecule to generate a reaction at a different position is an ongoing challenge in organic synthesis. Effective remote functionalization protocols have the potential to provide access to almost any derivatives but are difficult to achieve. The difficulty is more pronounced for acyclic systems where flexible alkyl chains are present between the initiating functional group and the desired reactive centres. In this Review, we discuss the concept of remote functionalization of alkenes using metal complexes, leading to a selective reaction at a position distal to the initial double bond. We aim to show the vast opportunity provided by this growing field through selected and representative examples. Our aim is to demonstrate that using a double bond as a chemical handle, metal-assisted long-distance activation could be used as a powerful synthetic strategy.

  5. Remote functionalization through alkene isomerization

    NASA Astrophysics Data System (ADS)

    Vasseur, Alexandre; Bruffaerts, Jeffrey; Marek, Ilan

    2016-03-01

    Exploiting the reactivity of one functional group within a molecule to generate a reaction at a different position is an ongoing challenge in organic synthesis. Effective remote functionalization protocols have the potential to provide access to almost any derivatives but are difficult to achieve. The difficulty is more pronounced for acyclic systems where flexible alkyl chains are present between the initiating functional group and the desired reactive centres. In this Review, we discuss the concept of remote functionalization of alkenes using metal complexes, leading to a selective reaction at a position distal to the initial double bond. We aim to show the vast opportunity provided by this growing field through selected and representative examples. Our aim is to demonstrate that using a double bond as a chemical handle, metal-assisted long-distance activation could be used as a powerful synthetic strategy.

  6. Biocatalytic desulfurization (BDS) of petrodiesel fuels.

    PubMed

    Mohebali, Ghasemali; Ball, Andrew S

    2008-08-01

    Oil refineries are facing many challenges, including heavier crude oils, increased fuel quality standards, and a need to reduce air pollution emissions. Global society is stepping on the road to zero-sulfur fuel, with only differences in the starting point of sulfur level and rate reduction of sulfur content between different countries. Hydrodesulfurization (HDS) is the most common technology used by refineries to remove sulfur from intermediate streams. However, HDS has several disadvantages, in that it is energy intensive, costly to install and to operate, and does not work well on refractory organosulfur compounds. Recent research has therefore focused on improving HDS catalysts and processes and also on the development of alternative technologies. Among the new technologies one possible approach is biocatalytic desulfurization (BDS). The advantage of BDS is that it can be operated in conditions that require less energy and hydrogen. BDS operates at ambient temperature and pressure with high selectivity, resulting in decreased energy costs, low emission, and no generation of undesirable side products. Over the last two decades several research groups have attempted to isolate bacteria capable of efficient desulfurization of oil fractions. This review examines the developments in our knowledge of the application of bacteria in BDS processes, assesses the technical viability of this technology and examines its future challenges.

  7. Biocatalytic removal of organic sulfur from coal

    SciTech Connect

    Webster, D.A.; Kilbane, J.J. II

    1994-09-09

    The objective is to characterize more completely the biochemical ability of the bacterium, Rhodococcus rhodochrous IGTS8, to cleave carbon-sulfur bonds with emphasis on data that will allow the development of a practical coal biodesulfurization process. Another approach for increasing the desulfurization activity of the IGTS8 cultures is to produce strains genetically that have higher activity. The goal of this part of research is to achieve strain improvement by introducing a stronger promoter using genetic engineering techniques. The promoter regulates the transcription of the genes for the desulfurization enzymes, and a stronger promoter, would up-regulate the expression of these genes, resulting in cells with higher desulfurization activity. Promoter probe vectors are used to identify and isolate promoters from a DNA library of the experimental organism. The major accomplishments have been to obtain high biodesulfurization activity in nonaqueous, media, especially using freeze-dried cells, and to have isolated strong promoters from R. rhodochrous IGTS8 which will be used to engineer the organism to produce strains with higher biocatalytic activity.

  8. Nanopropulsion by biocatalytic self-assembly.

    PubMed

    Leckie, Joy; Hope, Alexander; Hughes, Meghan; Debnath, Sisir; Fleming, Scott; Wark, Alastair W; Ulijn, Rein V; Haw, Mark D

    2014-09-23

    A number of organisms and organelles are capable of self-propulsion at the micro- and nanoscales. Production of simple man-made mimics of biological transportation systems may prove relevant to achieving movement in artificial cells and nano/micronscale robotics that may be of biological and nanotechnological importance. We demonstrate the propulsion of particles based on catalytically controlled molecular self-assembly and fiber formation at the particle surface. Specifically, phosphatase enzymes (acting as the engine) are conjugated to a quantum dot (the vehicle), and are subsequently exposed to micellar aggregates (fuel) that upon biocatalytic dephosphorylation undergo fibrillar self-assembly, which in turn causes propulsion. The motion of individual enzyme/quantum dot conjugates is followed directly using fluorescence microscopy. While overall movement remains random, the enzyme-conjugates exhibit significantly faster transport in the presence of the fiber forming system, compared to controls without fuel, a non-self-assembling substrate, or a substrate which assembles into spherical, rather than fibrous structures upon enzymatic dephosphorylation. When increasing the concentration of the fiber-forming fuel, the speed of the conjugates increases compared to non-self-assembling substrate, although directionality remains random.

  9. Chemoenzymatic Epoxidation of Alkenes and Reusability Study of the Phenylacetic Acid

    PubMed Central

    Abdulmalek, Emilia; Mizan, Hanis Nabillah; Abdul Rahman, Mohd. Basyaruddin; Basri, Mahiran; Salleh, Abu Bakar

    2014-01-01

    Here, we focused on a simple enzymatic epoxidation of alkenes using lipase and phenylacetic acid. The immobilised Candida antarctica lipase B, Novozym 435 was used to catalyse the formation of peroxy acid instantly from hydrogen peroxide (H2O2) and phenylacetic acid. The peroxy phenylacetic acid generated was then utilised directly for in situ oxidation of alkenes. A variety of alkenes were oxidised with this system, resulting in 75–99% yield of the respective epoxides. On the other hand, the phenylacetic acid was recovered from the reaction media and reused for more epoxidation. Interestingly, the waste phenylacetic acid had the ability to be reused for epoxidation of the 1-nonene to 1-nonene oxide, giving an excellent yield of 90%. PMID:24587751

  10. Phosphabarrelenes as ligands in rhodium-catalyzed hydroformylation of internal alkenes essentially free of alkene isomerization.

    PubMed

    Fuchs, Evelyn; Keller, Manfred; Breit, Bernhard

    2006-09-06

    Despite significant research efforts in the past, one of the remaining problems to be solved in industrially important hydroformylation is the chemoselective low-pressure hydroformylation of internal alkenes. We report here on a new class of phosphabarrelene/rhodium catalysts 2 that display very high activity towards hydroformylation of internal alkenes with an unusually low tendency towards alkene isomerization. Preparation of new phosphabarrelene ligands, studies of their coordination properties, as well as results obtained in the rhodium-catalyzed hydroformylation of cyclic and acyclic internal alkenes are reported.

  11. Biocatalytic potential of laccase-like multicopper oxidases from Aspergillus niger

    PubMed Central

    2012-01-01

    Background Laccase-like multicopper oxidases have been reported in several Aspergillus species but they remain uncharacterized. The biocatalytic potential of the Aspergillus niger fungal pigment multicopper oxidases McoA and McoB and ascomycete laccase McoG was investigated. Results The laccase-like multicopper oxidases McoA, McoB and McoG from the commonly used cell factory Aspergillus niger were homologously expressed, purified and analyzed for their biocatalytic potential. All three recombinant enzymes were monomers with apparent molecular masses ranging from 80 to 110 kDa. McoA and McoG resulted to be blue, whereas McoB was yellow. The newly obtained oxidases displayed strongly different activities towards aromatic compounds and synthetic dyes. McoB exhibited high catalytic efficiency with N,N-dimethyl-p-phenylenediamine (DMPPDA) and 2,2-azino-di(3-ethylbenzthiazoline) sulfonic acid (ABTS), and appeared to be a promising biocatalyst. Besides oxidizing a variety of phenolic compounds, McoB catalyzed successfully the decolorization and detoxification of the widely used textile dye malachite green. Conclusions The A. niger McoA, McoB, and McoG enzymes showed clearly different catalytic properties. Yellow McoB showed broad substrate specificity, catalyzing the oxidation of several phenolic compounds commonly present in different industrial effluents. It also harbored high decolorization and detoxification activity with the synthetic dye malachite green, showing to have an interesting potential as a new industrial biocatalyst. PMID:23270588

  12. Biocatalytic Reductions of Baylis - Hillman Adducts

    SciTech Connect

    A Walton; W Conerly; Y Pompeu; B Sullivan; J Stewart

    2011-12-31

    Baylis-Hillman adducts are highly useful synthetic intermediates; to enhance their value further, we sought enantiocomplementary alkene reductases to introduce chirality. Two solutions emerged: (1) a wild-type protein from Pichia stipitis (OYE 2.6), whose performance significantly outstrips that of the standard enzyme (Saccharomyces pastorianus OYE1), and (2) a series of OYE1 mutants at position 116 (Trp in the wild-type enzyme). To understand how mutations could lead to inverted enantioselectivity, we solved the X-ray crystal structure of the Trp116Ile OYE1 variant complexed with a cyclopentenone substrate. This revealed key protein-ligand interactions that control the orientation of substrate binding above the FMN cofactor.

  13. Vinylation of Unprotected Phenols Using a Biocatalytic System.

    PubMed

    Busto, Eduardo; Simon, Robert C; Kroutil, Wolfgang

    2015-09-07

    Readily available substituted phenols were coupled with pyruvate in buffer solution under atmospheric conditions to afford the corresponding para-vinylphenol derivatives while releasing only one molecule of CO2 and water as the by-products. This transformation was achieved by designing a biocatalytic system that combines three biocatalytic steps, namely the C-C coupling of phenol and pyruvate in the presence of ammonia, which leads to the corresponding tyrosine derivative, followed by deamination and decarboxylation. The biocatalytic transformation proceeded with high regioselectivity and afforded exclusively the desired para products. This method thus represents an environmentally friendly approach for the direct vinylation of readily available 2-, 3-, or 2,3-disubstituted phenols on preparative scale (0.5 mmol) that provides vinylphenols in high yields (65-83 %).

  14. Alkene anti-Dihydroxylation with Malonoyl Peroxides.

    PubMed

    Alamillo-Ferrer, Carla; Davidson, Stuart C; Rawling, Michael J; Theodoulou, Natalie H; Campbell, Matthew; Humphreys, Philip G; Kennedy, Alan R; Tomkinson, Nicholas C O

    2015-10-16

    Malonoyl peroxide 1, prepared in a single step from the commercially available diacid, is an effective reagent for the anti-dihydroxylation of alkenes. Reaction of 1 with an alkene in the presence of acetic acid at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (35-92%) with up to 13:1 anti-selectivity. A mechanism consistent with experimental findings is proposed that accounts for the selectivity observed.

  15. Biocatalytic Conversion of Avermectin to 4"-Oxo-Avermectin: Heterologous Expression of the ema1 Cytochrome P450 Monooxygenase

    PubMed Central

    Molnár, István; Hill, D. Steven; Zirkle, Ross; Hammer, Philip E.; Gross, Frank; Buckel, Thomas G.; Jungmann, Volker; Pachlatko, Johannes Paul; Ligon, James M.

    2005-01-01

    The cytochrome P450 monooxygenase Ema1 from Streptomyces tubercidicus R-922 and its homologs from closely related Streptomyces strains are able to catalyze the regioselective oxidation of avermectin into 4"-oxo-avermectin, a key intermediate in the manufacture of the agriculturally important insecticide emamectin benzoate (V. Jungmann, I. Molnár, P. E. Hammer, D. S. Hill, R. Zirkle, T. G. Buckel, D. Buckel, J. M. Ligon, and J. P. Pachlatko, Appl. Environ. Microbiol. 71:6968-6976, 2005). The gene for Ema1 has been expressed in Streptomyces lividans, Streptomyces avermitilis, and solvent-tolerant Pseudomonas putida strains using different promoters and vectors to provide biocatalytically competent cells. Replacing the extremely rare TTA codon with the more frequent CTG codon to encode Leu4 in Ema1 increased the biocatalytic activities of S. lividans strains producing this enzyme. Ferredoxins and ferredoxin reductases were also cloned from Streptomyces coelicolor and biocatalytic Streptomyces strains and tested in ema1 coexpression systems to optimize the electron transport towards Ema1. PMID:16269733

  16. Sequential lignin depolymerization by combination of biocatalytic and formic acid/formate treatment steps.

    PubMed

    Gasser, Christoph A; Čvančarová, Monika; Ammann, Erik M; Schäffer, Andreas; Shahgaldian, Patrick; Corvini, Philippe F-X

    2017-03-01

    Lignin, a complex three-dimensional amorphous polymer, is considered to be a potential natural renewable resource for the production of low-molecular-weight aromatic compounds. In the present study, a novel sequential lignin treatment method consisting of a biocatalytic oxidation step followed by a formic acid-induced lignin depolymerization step was developed and optimized using response surface methodology. The biocatalytic step employed a laccase mediator system using the redox mediator 1-hydroxybenzotriazole. Laccases were immobilized on superparamagnetic nanoparticles using a sorption-assisted surface conjugation method allowing easy separation and reuse of the biocatalysts after treatment. Under optimized conditions, as much as 45 wt% of lignin could be solubilized either in aqueous solution after the first treatment or in ethyl acetate after the second (chemical) treatment. The solubilized products were found to be mainly low-molecular-weight aromatic monomers and oligomers. The process might be used for the production of low-molecular-weight soluble aromatic products that can be purified and/or upgraded applying further downstream processes.

  17. Biocatalytic Refining of Soybean Oil into Cosmeceutical Ingredients

    USDA-ARS?s Scientific Manuscript database

    Our mission is to develop new, value-added uses for commodity crops and oils. We chose to fulfill this mission while adhering as closely as possible to the tenants of “green” chemistry. We have developed patented, all-natural oils called Feruloyl Soy Glycerols (FSG) from the biocatalytic transester...

  18. Biocatalytic Characterization of Human FMO5: Unearthing Baeyer-Villiger Reactions in Humans.

    PubMed

    Fiorentini, Filippo; Geier, Martina; Binda, Claudia; Winkler, Margit; Faber, Kurt; Hall, Mélanie; Mattevi, Andrea

    2016-04-15

    Flavin-containing mono-oxygenases are known as potent drug-metabolizing enzymes, providing complementary functions to the well-investigated cytochrome P450 mono-oxygenases. While human FMO isoforms are typically involved in the oxidation of soft nucleophiles, the biocatalytic activity of human FMO5 (along its physiological role) has long remained unexplored. In this study, we demonstrate the atypical in vitro activity of human FMO5 as a Baeyer-Villiger mono-oxygenase on a broad range of substrates, revealing the first example to date of a human protein catalyzing such reactions. The isolated and purified protein was active on diverse carbonyl compounds, whereas soft nucleophiles were mostly non- or poorly reactive. The absence of the typical characteristic sequence motifs sets human FMO5 apart from all characterized Baeyer-Villiger mono-oxygenases so far. These findings open new perspectives in human oxidative metabolism.

  19. A General Approach to Catalytic Alkene Anti-Markovnikov Hydrofunctionalization Reactions via Acridinium Photoredox Catalysis.

    PubMed

    Margrey, Kaila A; Nicewicz, David A

    2016-09-20

    The development of methods for anti-Markovnikov alkene hydrofunctionalization has been a focal point of catalysis research for several decades. The vast majority of work on the control of regioselectivity for this reaction class has hinged on transition metal catalyst activation of olefin substrates. While progress has been realized, there are significant limitations to this approach, and a general solution for catalysis of anti-Markovnikov hydrofunctionalization reactions of olefins does not presently exist. In the past several years, this research lab has focused on alkene activation by single electron oxidation using organic photoredox catalysts to facilitate anti-Markovnikov hydrofunctionalization. By accessing reactive cation radical intermediates, we have realized a truly general approach to anti-Markovnikov olefin hydrofunctionalization reactions. We have identified a dual organic catalyst system consisting of an acridinium photooxidant, first reported by Fukuzumi, and a redox-active hydrogen atom donor that accomplishes a wide range of hydrofunctionalization reactions with complete anti-Markovnikov regiocontrol. This method relies on single electron oxidation of the alkene to reverse its polarity and results in the opposite regioselectivity for hydrofunctionalization. In 2012, we disclosed the anti-Markovnikov hydroetherification of alkenols employing an acridinium photocatalyst and a hydrogen atom donor that proceeds via interwoven polar and radical steps. This general catalyst system has enabled several important reactions in this area, including anti-Markovnikov alkene hydroacetoxylation, hydrolactonization, hydroamination, and hydrotrifluoromethylation reactions. More recently, we have also delineated conditions for intermolecular anti-Markovnikov hydroamination reactions of alkenes using either triflamide or nitrogen-containing heteroaromatic compounds such as pyrazole, indazole, imidazole, and 1,2,3-triazole. Further development led to a method for

  20. Heterogeneous Catalysis: The Horiuti-Polanyi Mechanism and Alkene Hydrogenation

    ERIC Educational Resources Information Center

    Mattson, Bruce; Foster, Wendy; Greimann, Jaclyn; Hoette, Trisha; Le, Nhu; Mirich, Anne; Wankum, Shanna; Cabri, Ann; Reichenbacher, Claire; Schwanke, Erika

    2013-01-01

    The hydrogenation of alkenes by heterogeneous catalysts has been studied for 80 years. The foundational mechanism was proposed by Horiuti and Polanyi in 1934 and consists of three steps: (i) alkene adsorption on the surface of the hydrogenated metal catalyst, (ii) hydrogen migration to the beta-carbon of the alkene with formation of a delta-bond…

  1. 40 CFR 721.10508 - Alkene substituted Bis phenol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkene substituted Bis phenol (generic... Specific Chemical Substances § 721.10508 Alkene substituted Bis phenol (generic). (a) Chemical substance... alkene substituted bis phenol (PMN P-07-161) is subject to reporting under this section for the...

  2. 40 CFR 721.10508 - Alkene substituted Bis phenol (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkene substituted Bis phenol (generic... Specific Chemical Substances § 721.10508 Alkene substituted Bis phenol (generic). (a) Chemical substance... alkene substituted bis phenol (PMN P-07-161) is subject to reporting under this section for the...

  3. Heterogeneous Catalysis: The Horiuti-Polanyi Mechanism and Alkene Hydrogenation

    ERIC Educational Resources Information Center

    Mattson, Bruce; Foster, Wendy; Greimann, Jaclyn; Hoette, Trisha; Le, Nhu; Mirich, Anne; Wankum, Shanna; Cabri, Ann; Reichenbacher, Claire; Schwanke, Erika

    2013-01-01

    The hydrogenation of alkenes by heterogeneous catalysts has been studied for 80 years. The foundational mechanism was proposed by Horiuti and Polanyi in 1934 and consists of three steps: (i) alkene adsorption on the surface of the hydrogenated metal catalyst, (ii) hydrogen migration to the beta-carbon of the alkene with formation of a delta-bond…

  4. A new approach to the deposition of nanostructured biocatalytic films

    NASA Astrophysics Data System (ADS)

    Troitsky, V. I.; Berzina, T. S.; Pastorino, L.; Bernasconi, E.; Nicolini, C.

    2003-06-01

    In the present work, monolayer engineering was used to fabricate biocatalytic nanostructured thin films based on the enzyme penicillin G acylase. The biocatalytic films with enhanced characteristics were produced by the deposition of alternate-layer assemblies with a predetermined structure using a combination of Langmuir-Blodgett and adsorption techniques. The value of enzyme activity and the level of protein detachment were measured in dependence on the variation of film composition and on the sequence of layer alternation. As a result, highly active and stable structures were found, which could be promising candidates for practical applications. The method of modification of the deposition method to provide continuous film formation on large-area supports is discussed.

  5. Alkene epoxidation employing metal nitro complexes

    DOEpatents

    Andrews, M.A.; Cheng, C.W.; Kelley, K.P.

    1982-07-15

    Process for converting alkenes to form epoxides utilizes transition metal nitro complexes of the formula: M(RCN)/sub 2/XNO/sub 2/ wherein M is palladium or platinum, R is an alkyl or aryl group containing up to 12 carbon atoms, and X is a monoanionic, monodentate ligand such as chlorine, optionally in the presence of molecular oxygen.

  6. Catalytic intermolecular alkene oxyamination with nitrenes.

    PubMed

    Dequirez, Geoffroy; Ciesielski, Jennifer; Retailleau, Pascal; Dauban, Philippe

    2014-07-14

    The Rh(II)-catalyzed intermolecular addition of nitrenes to aromatic and aliphatic alkenes provides vicinal amino alcohols with yields of up to 95 % and complete regioselectivity. This 1,2-oxyamination reaction involves the formation of an aziridine intermediate that undergoes in situ ring opening. The latter is induced by the Rh-bound nitrene that behaves as a Lewis acid.

  7. Biocatalytic Buffering System for Detoxification of Nerve Agents

    DTIC Science & Technology

    2005-11-30

    Organization (10 g of agent per m2), the concentration of agent in detergent and microemulsion systems, which typically consist of 1 to 10 vol... microemulsions and nanoemulsions. A portion of our efforts was focused towards assessing the use of biocatalytic pH control in these types of mediums...not accurately measure pH of the water core of micelles in a model water-in-oil microemulsion comprised of 13 vol % Tween 85, 8 vol % isopropanol

  8. An alkene-promoted borane-catalyzed highly stereoselective hydrogenation of alkynes to give Z- and E-alkenes.

    PubMed

    Liu, Yongbing; Hu, Lianrui; Chen, Hui; Du, Haifeng

    2015-02-16

    The stereoselective hydrogenation of alkynes to alkenes is an extremely useful transformation in synthetic chemistry. Despite numerous reports for the synthesis of Z-alkenes, the hydrogenation of alkynes to give E-alkenes is still not well resolved. In particular, selective preparation of both Z- and E-alkenes by the same catalytic hydrogenation system using molecular H2 has rarely been reported. In this paper, a novel strategy of using simple alkenes as promoters for the HB(C6 F5 )2 -catalyzed metal-free hydrogenation of alkynes was adopted. Significantly, both Z- and E-alkenes can be furnished by hydrogenation with molecular H2 in high yields with excellent stereoselectivities. Further experimental and theoretical mechanistic studies suggest that interactions between H and F atoms of the alkene promoter, borane intermediate, and H2 play an essential role in promoting the hydrogenolysis reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Recent biocatalytic oxidation–reduction cascades

    PubMed Central

    Schrittwieser, Joerg H; Sattler, Johann; Resch, Verena; Mutti, Francesco G; Kroutil, Wolfgang

    2011-01-01

    The combination of an oxidation and a reduction in a cascade allows performing transformations in a very economic and efficient fashion. The challenge is how to combine an oxidation with a reduction in one pot, either by running the two reactions simultaneously or in a stepwise fashion without isolation of intermediates. The broader availability of various redox enzymes nowadays has triggered the recent investigation of various oxidation–reduction cascades. PMID:21130024

  10. Rhodium-Catalyzed Alkene Difunctionalization with Nitrenes.

    PubMed

    Ciesielski, Jennifer; Dequirez, Geoffroy; Retailleau, Pascal; Gandon, Vincent; Dauban, Philippe

    2016-06-27

    The Rh(II) -catalyzed oxyamination and diamination of alkenes generate 1,2-amino alcohols and 1,2-diamines, respectively, in good to excellent yields and with complete regiocontrol. In the case of diamination, the intramolecular reaction provides an efficient method for the preparation of pyrrolidines, and the intermolecular reaction produces vicinal amines with orthogonal protecting groups. These alkene difunctionalizations proceed by aziridination followed by nucleophilic ring opening induced by an Rh-bound nitrene generated in situ, details of which were uncovered by both experimental and theoretical studies. In particular, DFT calculations show that the nitrogen atom of the putative [Rh]2 =NR metallanitrene intermediate is electrophilic and support an aziridine activation pathway by N⋅⋅⋅N=[Rh]2 bond formation, in addition to the N⋅⋅⋅[Rh]2 =NR coordination mode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Methods for direct alkene diamination, new & old

    PubMed Central

    de Jong, Sam; Nosal, Daniel G.; Wardrop, Duncan J.

    2012-01-01

    The 1,2-diamine moiety is a ubiquitous structural motif present in a wealth of natural products, including non-proteinogenic amino acids and numerous alkaloids, as well as in pharmaceutical agents, chiral ligands and organic reagents. The biological activity associated with many of these systems and their chemical utility in general has ensured that the development of methods for their preparation is of critical importance. While a wide range of strategies for the preparation of 1,2-diamines have been established, the diamination of alkenes offers a particularly direct and efficient means of accessing these systems. The purpose of this review is to provide an overview of all methods of direct alkene diamination, metal-mediated or otherwise. PMID:22888177

  12. Alkene metathesis: the search for better catalysts.

    PubMed

    Deshmukh, Prashant H; Blechert, Siegfried

    2007-06-28

    Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

  13. Palladium-catalyzed vinylation of aminals with simple alkenes: a new strategy to construct allylamines.

    PubMed

    Xie, Yinjun; Hu, Jianhua; Wang, Yanyu; Xia, Chungu; Huang, Hanmin

    2012-12-26

    A novel, highly selective palladium-catalyzed vinylation reaction for the direct synthesis of allylic amines from styrenes and aminals has been established. The utility of this method was also demonstrated by the rapid synthesis of cinnarizine from aldehydes, amines, and simple alkenes in one-pot manner. Mechanistic studies suggested that the reaction proceeds through a valuable cyclometalated Pd(II) complex generated by the oxidative addition of aminal to a Pd(0) species.

  14. One-Pot Strategy for Thiazoline Synthesis from Alkenes and Thioamides.

    PubMed

    Alom, Nur-E; Wu, Fan; Li, Wei

    2017-02-17

    A convenient synthesis of a privileged pharmaceutical motif, thiazoline is accomplished. This reaction utilizes simple and readily available alkene and thioamide substrates in an intermolecular fashion via a simple one-pot procedure. A wide range of functional groups is tolerated, and the thiazoline product has been further utilized for the synthesis of the corresponding β-aminothiol and thiazole from routine hydrolysis and oxidation protocols.

  15. The role of salicylic acid, L-ascorbic acid and oxalic acid in promoting the oxidation of alkenes with H2O2 catalysed by [MnIV2(O)3(tmtacn)2]2+.

    PubMed

    de Boer, Johannes W; Alsters, Paul L; Meetsma, Auke; Hage, Ronald; Browne, Wesley R; Feringa, Ben L

    2008-11-28

    The role played by the additives salicylic acid, L-ascorbic acid and oxalic acid in promoting the catalytic activity of [MnIV2(O)3(tmtacn)2](PF6)2 (1(PF6)2, where tmtacn = N,N',N''-trimethyl-1,4,7-triazacyclononane) in the epoxidation and cis-dihydroxylation of alkenes with H2O2 and in suppressing the catalysed decomposition of H2O2 is examined. Whereas aliphatic and aromatic carboxylic acids effect enhancement of the catalytic activity of 1 through the in situ formation dinuclear carboxylato bridged complexes of the type [MnIII2(mu-O)(mu-RCO2)2(tmtacn)2]2+, for L-ascorbic acid and oxalic acid notable differences in reactivity are observed. Although for L-ascorbic acid key differences in the spectroscopic properties of the reaction mixtures are observed compared with carboxylic acids, the involvement of carboxylic acids formed in situ is apparent. For oxalic acid the situation is more complex with two distinct catalyst systems in operation; the first, which engages in epoxidation only, is dominant until the oxalic acid additive is consumed completely at which point carboxylic acids formed in situ take on the role of additives to form a second distinct catalyst system, i.e. that which was observed for alkyl and aromatic carboxylic acids, which yield both cis-diol and epoxide products.

  16. Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent.

    PubMed

    Ashtekar, Kumar Dilip; Vetticatt, Mathew; Yousefi, Roozbeh; Jackson, James E; Borhan, Babak

    2016-07-06

    Emerging work on organocatalytic enantioselective halocyclizations naturally draws on conditions where both new bonds must be formed under delicate control, the reaction regime where the concerted nature of the AdE3 mechanism is of greatest importance. Without assistance, many simple alkene substrates react slowly or not at all with conventional halenium donors under synthetically relevant reaction conditions. As demonstrated earlier by Shilov, Cambie, Williams, Fahey, and others, alkenes can undergo a concerted AdE3-type reaction via nucleophile participation, which sets the configuration of the newly created stereocenters at both ends in one step. Herein, we explore the modulation of alkene reactivity and halocyclization rates by nucleophile proximity and basicity, through detailed analyses of starting material spectroscopy, addition stereopreferences, isotope effects, and nucleophile-alkene interactions, all obtained in a context directly relevant to synthesis reaction conditions. The findings build on the prior work by highlighting the reactivity spectrum of halocyclizations from stepwise to concerted, and suggest strategies for design of new reactions. Alkene reactivity is seen to span the range from the often overgeneralized "sophomore textbook" image of stepwise electrophilic attack on the alkene and subsequent nucleophilic bond formation, to the nucleophile-assisted alkene activation (NAAA) cases where electron donation from the nucleophilic addition partner activates the alkene for electrophilic attack. By highlighting the factors that control reactivity across this range, this study suggests opportunities to explain and control stereo-, regio-, and organocatalytic chemistry in this important class of alkene additions.

  17. Copper-catalyzed alkene arylation with diaryliodonium salts.

    PubMed

    Phipps, Robert J; McMurray, Lindsay; Ritter, Stefanie; Duong, Hung A; Gaunt, Matthew J

    2012-07-04

    Alkenes and arenes represent two classes of feedstock compounds whose union has fundamental importance to synthetic organic chemistry. We report a new approach to alkene arylation using diaryliodonium salts and Cu catalysis. Using a range of simple alkenes, we have shown that the product outcomes differ significantly from those commonly obtained by the Heck reaction. We have used these insights to develop a number of new tandem and cascade reactions that transform readily available alkenes into complex arylated products that may have broad applications in chemical synthesis.

  18. Biocatalytic approaches applied to the synthesis of nucleoside prodrugs.

    PubMed

    Iglesias, Luis E; Lewkowicz, Elizabeth S; Medici, Rosario; Bianchi, Paola; Iribarren, Adolfo M

    2015-01-01

    Nucleosides are valuable bioactive molecules, which display antiviral and antitumour activities. Diverse types of prodrugs are designed to enhance their therapeutic efficacy, however this strategy faces the troublesome selectivity issues of nucleoside chemistry. In this context, the aim of this review is to give an overview of the opportunities provided by biocatalytic procedures in the preparation of nucleoside prodrugs. The potential of biocatalysis in this research area will be presented through examples covering the different types of nucleoside prodrugs: nucleoside analogues as prodrugs, nucleoside lipophilic prodrugs and nucleoside hydrophilic prodrugs.

  19. Biocatalytic routes to chiral amines and amino acids.

    PubMed

    Gotor-Fernández, Vicente; Gotor, Vicente

    2009-11-01

    Biocatalysis is a well-known and well-established technology that allows clean and straightforward stereoselective transformations to be conducted under mild reaction conditions. Traditionally, hydrolases, oxidoreductases and lyases have been used for these transformations to give the final products in excellent yields and with a high level of enantiopurity. Particular attention has been focused on biocatalytic routes because of the increasing demand for economic and environmentally friendly processes for the manufacture of single enantiomer drugs and high added-value compounds by the industrial sector. Recent advances in the field of biotransformations applied to the production of chiral amines and amino acids are reviewed.

  20. Hydroxy functionalization of non-activated C-H and C=C bonds: new perspectives for the synthesis of alcohols through biocatalytic processes.

    PubMed

    Gröger, Harald

    2014-03-17

    New perspectives through enzymes: Recent breakthroughs have been achieved in the selective hydroxy functionalization of non-activated C-H and C=C bonds. Enzymes turned out to be suitable catalysts for the ω-hydroxylation of (substituted) alkanes and regioselective hydroxylation of aromatic hydrocarbons with atmospheric oxygen as the oxidant, and the asymmetric addition of water to non-activated alkenes.

  1. Reversible Interconversion between Alkanes, Alkenes, Alcohols and Ketones under Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Shipp, J.; Hartnett, H. E.; Gould, I. R.; Shock, E.; Williams, L. B.

    2011-12-01

    Many transformation reactions involving hydrocarbons that occur in deep sedimentary systems and determine petroleum compositions occur in the presence of H2O. Hydrothermal transformations of organic material are thought to provide carbon sources for microbes in deep ocean sediments. Hydrothermal conditions may also mimic the conditions where life developed on an early Earth. Nevertheless, much remains to be learned about the mechanisms of hydrothermal organic reactions, including ways in which various reactions are interrelated and how reactions compete with each other. It can be argued that metastable equilibrium states develop over geological timescales and at geochemically relevant temperatures, suggesting that reactions occur under thermodynamic rather than kinetic control. The extent to which reactions are reversible, and how product distributions are determined, are primary tests of the metastable equilibrium model. Seewald (2001, GCA 65, 1641-1664) showed that under hydrothermal conditions and in the presence of a redox buffer, simple alkanes and alkenes undergo oxidation, reduction, and hydration reactions. He proposed a reaction scheme where alkanes interconvert with alkenes, followed by stepwise hydration of alkenes to alcohols, oxidation to ketones, and finally conversion to carboxylic acids, which can undergo decarboxylation. Here we describe experiments that further develop the scope of these functional group interconversions, determine relative reaction kinetics, and provide insight into competing reactions. Hydrothermal experiments were performed at 300°C and 100 MPa in gold capsules for 12 to 144 hours. The reactant structures were based on cyclohexane with one and two methyl groups that served as regio- and stereochemical markers for the reactions. Starting with the alkanes, the observed products include the corresponding alkenes, alcohols, ketones and enones, in support of the Seewald reaction scheme. Our experiments add a branch to this scheme

  2. Bio-catalytic nanocompartments for in situ production of glucose-6-phosphate.

    PubMed

    Lomora, M; Gunkel-Grabole, G; Mantri, S; Palivan, C G

    2017-08-29

    Cells are sophisticated biocatalytic systems driving a complex network of biochemical reactions. A bioinspired strategy to create advanced functional systems is to design confined spaces for complex enzymatic reactions by using a combination of synthetic polymer assemblies and natural cell components. Here, we developed bio-catalytic nanocompartments that contain phosphoglucomutase protected by a biomimetic polymer membrane, which was permeabilized for reactants through insertion of an engineered α-hemolysin pore protein. These bio-catalytic nanocompartments serve for production of glucose-6-phosphate, and thus possess great potential for applications in an incomplete glycolysis, pentose phosphate pathway, or in plant biological reactions.

  3. The Pressure Dependency of Stabilized Criegee Intermediate Yields of Selected Ozone-Alkene Reactions

    NASA Astrophysics Data System (ADS)

    Hakala, J. P.; Donahue, N. M.

    2014-12-01

    Stabilized Criegee Intermediates (SCI) play an important role as an oxidizing species in atmospheric reactions. The ozonolysis of alkenes in the atmosphere, i.e. the mechanism by which the SCIs are produced, is a major pathway to the formation of Secondary Organic Aerosols (SOA) in the atmosphere. Just how much SCIs contribute to the SOA formation is not well known and fundamental research in the kinetics of SCI formation need to be performed to shed light on this mystery. The alkene ozonolysis is highly exothermic reaction, so a third body is needed for stabilizing the SCI, thus making the SCI yield pressure dependent. We studied the production of SCIs at different pressures by studying their ability to oxidize sulfur dioxide in a pressure controlled flow reactor. We used a mixture of ultra-high purity nitrogen, oxygen, and a selective scavenger for hydroxyl radical (OH) as a carrier gas, and injected a mixture of nitrogen, sulfur dioxide and selected alkene to the center of the flow for ozonolysis to take place. With the OH radical scavenged, the SCI yield of the reaction was measured by measuring the amount of sulfuric acid formed in the reaction between SCI and sulfur dioxide with a Chemical Ionization Mass Spectrometer (CIMS). This work was supported by NASA/ROSES grant NNX12AE54G to CMU and Academy of Finland Center of Excellence project 1118615.

  4. Osmium-free direct syn-dihydroxylation of alkenes.

    PubMed

    Bataille, Carole J R; Donohoe, Timothy J

    2011-01-01

    Numerous synthetic protocols for producing syn-diols from the corresponding alkenes have been developed and published over recent years. It is the intent of the following tutorial review to present a concise summary of the main methods used to prepare syn-diol fragments directly from alkene precursors, and that do not make use of osmium oxo complexes as catalysts.

  5. Stereoselective halocyclization of alkenes with N-acyl hemiaminal nucleophiles.

    PubMed

    Liu, Na; Wang, Hao-Yuan; Zhang, Wei; Jia, Zhi-Hong; Guzei, Ilia A; Xu, Hua-Dong; Tang, Weiping

    2013-11-01

    Halocyclization of alkenes was realized using N-acylhemiaminal nucleophiles. High diastereoselectivity could be achieved for the formation of three stereogenic centers in this halogen-mediated cyclization reaction. We also demonstrated that enantioselective bromocyclization of alkenes using N-acylhemiaminal nucleophiles was possible. © 2013 Wiley Periodicals, Inc.

  6. Catalytic Determinants of Alkene Production by the Cytochrome P450 Peroxygenase OleTJE*

    PubMed Central

    Matthews, Sarah; Belcher, James D.; Tee, Kang Lan; Girvan, Hazel M.; McLean, Kirsty J.; Rigby, Stephen E. J.; Levy, Colin W.; Leys, David; Parker, David A.; Blankley, Richard T.; Munro, Andrew W.

    2017-01-01

    The Jeotgalicoccus sp. peroxygenase cytochrome P450 OleTJE (CYP152L1) is a hydrogen peroxide-driven oxidase that catalyzes oxidative decarboxylation of fatty acids, producing terminal alkenes with applications as fine chemicals and biofuels. Understanding mechanisms that favor decarboxylation over fatty acid hydroxylation in OleTJE could enable protein engineering to improve catalysis or to introduce decarboxylation activity into P450s with different substrate preferences. In this manuscript, we have focused on OleTJE active site residues Phe79, His85, and Arg245 to interrogate their roles in substrate binding and catalytic activity. His85 is a potential proton donor to reactive iron-oxo species during substrate decarboxylation. The H85Q mutant substitutes a glutamine found in several peroxygenases that favor fatty acid hydroxylation. H85Q OleTJE still favors alkene production, suggesting alternative protonation mechanisms. However, the mutant undergoes only minor substrate binding-induced heme iron spin state shift toward high spin by comparison with WT OleTJE, indicating the key role of His85 in this process. Phe79 interacts with His85, and Phe79 mutants showed diminished affinity for shorter chain (C10–C16) fatty acids and weak substrate-induced high spin conversion. F79A OleTJE is least affected in substrate oxidation, whereas the F79W/Y mutants exhibit lower stability and cysteine thiolate protonation on reduction. Finally, Arg245 is crucial for binding the substrate carboxylate, and R245E/L mutations severely compromise activity and heme content, although alkene products are formed from some substrates, including stearic acid (C18:0). The results identify crucial roles for the active site amino acid trio in determining OleTJE catalytic efficiency in alkene production and in regulating protein stability, heme iron coordination, and spin state. PMID:28053093

  7. Catalytic Determinants of Alkene Production by the Cytochrome P450 Peroxygenase OleTJE.

    PubMed

    Matthews, Sarah; Belcher, James D; Tee, Kang Lan; Girvan, Hazel M; McLean, Kirsty J; Rigby, Stephen E J; Levy, Colin W; Leys, David; Parker, David A; Blankley, Richard T; Munro, Andrew W

    2017-03-24

    The Jeotgalicoccus sp. peroxygenase cytochrome P450 OleTJE (CYP152L1) is a hydrogen peroxide-driven oxidase that catalyzes oxidative decarboxylation of fatty acids, producing terminal alkenes with applications as fine chemicals and biofuels. Understanding mechanisms that favor decarboxylation over fatty acid hydroxylation in OleTJE could enable protein engineering to improve catalysis or to introduce decarboxylation activity into P450s with different substrate preferences. In this manuscript, we have focused on OleTJE active site residues Phe(79), His(85), and Arg(245) to interrogate their roles in substrate binding and catalytic activity. His(85) is a potential proton donor to reactive iron-oxo species during substrate decarboxylation. The H85Q mutant substitutes a glutamine found in several peroxygenases that favor fatty acid hydroxylation. H85Q OleTJE still favors alkene production, suggesting alternative protonation mechanisms. However, the mutant undergoes only minor substrate binding-induced heme iron spin state shift toward high spin by comparison with WT OleTJE, indicating the key role of His(85) in this process. Phe(79) interacts with His(85), and Phe(79) mutants showed diminished affinity for shorter chain (C10-C16) fatty acids and weak substrate-induced high spin conversion. F79A OleTJE is least affected in substrate oxidation, whereas the F79W/Y mutants exhibit lower stability and cysteine thiolate protonation on reduction. Finally, Arg(245) is crucial for binding the substrate carboxylate, and R245E/L mutations severely compromise activity and heme content, although alkene products are formed from some substrates, including stearic acid (C18:0). The results identify crucial roles for the active site amino acid trio in determining OleTJE catalytic efficiency in alkene production and in regulating protein stability, heme iron coordination, and spin state.

  8. Electrophilic Addition to Alkenes: The Relation between Reactivity and Enthalpy of Hydrogenation: Regioselectivity is Determined by the Stability of the Two Conceivable Products.

    PubMed

    Schnatter, Wayne F K; Rogers, Donald W; Zavitsas, Andreas A

    2015-07-13

    Although electrophilic addition to alkenes has been well studied, some secrets still remain. Halogenations, hydrohalogenations, halohydrin formations, hydrations, epoxidations, other oxidations, carbene additions, and ozonolyses are investigated to elucidate the relation of alkene reactivities with their enthalpies of hydrogenation (ΔHhyd ). For addition of electrophiles to unconjugated hydrocarbon alkenes, ln(k) is a linear function of ΔHhyd , where k is the rate constant. Linear correlation coefficients are about 0.98 or greater. None of the many previously proposed correlations of ln(k) with the properties of alkenes or with linear free-energy relationships match the generality and accuracy of the simple linear relationship found herein. A notable exception is acid-catalyzed hydration in water or in solvents stabilizing relatively stable carbocation intermediates (e.g., tertiary, benzylic, or allylic). (13) C NMR chemical shifts of the two alkene carbons also predict regioselectivity. These effects have not been noted previously and are operative in general, including addition to heteroatom-substituted alkenes.

  9. Products and Kinetics of the Reactions of an Alkane Monolayer and a Terminal Alkene Monolayer with NO₃ Radicals

    SciTech Connect

    Gross, Simone; Bertram, Allan K.

    2009-01-27

    The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO₃ radicals (in the presence of NO₂ and O₂) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO₂). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO₃ radicals. The reactive uptake coefficient (g) of NO₃ on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the g value determined in our studies, we show that under conditions where NO₃ is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO₃. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.

  10. Products and kinetics of the reactions of an alkane monolayer and a terminal alkene monolayer with NO3 radicals

    NASA Astrophysics Data System (ADS)

    Gross, Simone; Bertram, Allan K.

    2009-01-01

    The reactions of an alkanethiol and a terminal alkenethiol self-assembled monolayer with NO3 radicals (in the presence of NO2 and O2) were studied. For the alkane monolayer, infrared (IR) spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the formation of organonitrates (RONO2). The observation of organonitrates is in contrast to the recent X-ray photoelectron spectroscopy (XPS) data, which showed very little nitrogen-containing surface species. The identification of organonitrates may help explain why significant volatilization of the organic chain was not observed in recent studies of alkane monolayer oxidation by NO3 radicals. The reactive uptake coefficient (γ) of NO3 on alkene monolayers determined in our study is higher than the values obtained in a recent study using liquid and solid alkene bulk films. A possible reason for this difference may be the location of the double bond at the interface. Using the γ value determined in our studies, we show that under conditions where NO3 is high the lifetime of an alkene monolayer in the atmosphere may be short (approximately 20 min). XPS, IR, and ToF-SIMS were used to identify surface functional groups after the oxidation of the alkene monolayers by NO3. The results are consistent with the formation of C-O, aldehyde/ketone, carboxylic groups, and nitrogen containing species.

  11. Mechanistic Studies of Wacker-Type Amidocyclization of Alkenes Catalyzed by (IMes)Pd(TFA)2(H2O): Kinetic and Stereochemical Implications of Proton Transfer†

    PubMed Central

    Ye, Xuan; White, Paul B.

    2012-01-01

    The stereochemical course of the amidopalladation of alkenes has important implications for the development of enantioselective Pd-catalyzed “Wacker-type” oxidative amination of alkenes. We have recently shown that the addition of base (Na2CO3) can alter the stereochemical course of amidopalladation in the (IMes)Pd(TFA)2(H2O)-catalyzed aerobic oxidative amidation of alkene. In this study, the mechanism of (IMes)Pd(TFA)2(H2O)-catalyzed oxidative heterocyclization of (Z)-4-hexenyltosylamide was investigated in the presence and absence of exogenous base Na2CO3. The results reveal two parallel pathways in the absence of base: a cis-amidopalladation pathway with turnover-limiting deprotonation of the sulfonamide nucleophile, and a trans-amidopalladation pathway with turnover-limiting nucleophilic attack of sulfonamide on the coordinated alkene. The addition of base (Na2CO3) lowers the energy barrier associated with the proton transfer, leading to an overall faster turnover rate and exclusive cis-amidopalladation of alkene. PMID:23157332

  12. Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.

    PubMed

    Ye, Xuan; White, Paul B; Stahl, Shannon S

    2013-03-01

    The stereochemical course of the amidopalladation of alkenes has important implications for the development of enantioselective Pd-catalyzed "Wacker-type" oxidative amidation of alkenes. We have recently shown that the addition of base (Na2CO3) can alter the stereochemical course of amidopalladation in the (IMes)Pd(TFA)2(H2O)-catalyzed aerobic oxidative amidation of alkene. In this study, the mechanism of (IMes)Pd(TFA)2(H2O)-catalyzed oxidative heterocyclization of (Z)-4-hexenyltosylamide was investigated in the presence and absence of exogenous base Na2CO3. The results reveal two parallel pathways in the absence of base: a cis-amidopalladation pathway with turnover-limiting deprotonation of the sulfonamide nucleophile and a trans-amidopalladation pathway with turnover-limiting nucleophilic attack of sulfonamide on the coordinated alkene. The addition of base (Na2CO3) lowers the energy barrier associated with the proton transfer, leading to an overall faster turnover rate and exclusive cis-amidopalladation of alkene.

  13. Microfluidic multi-input reactor for biocatalytic synthesis using transketolase☆

    PubMed Central

    Lawrence, James; O'Sullivan, Brian; Lye, Gary J.; Wohlgemuth, Roland; Szita, Nicolas

    2013-01-01

    Biocatalytic synthesis in continuous-flow microreactors is of increasing interest for the production of specialty chemicals. However, the yield of production achievable in these reactors can be limited by the adverse effects of high substrate concentration on the biocatalyst, including inhibition and denaturation. Fed-batch reactors have been developed in order to overcome this problem, but no continuous-flow solution exists. We present the design of a novel multi-input microfluidic reactor, capable of substrate feeding at multiple points, as a first step towards overcoming these problems in a continuous-flow setting. Using the transketolase-(TK) catalysed reaction of lithium hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose (ERY), we demonstrate the transposition of a fed-batch substrate feeding strategy to our microfluidic reactor. We obtained a 4.5-fold increase in output concentration and a 5-fold increase in throughput compared with a single input reactor. PMID:24187515

  14. Microfluidic multi-input reactor for biocatalytic synthesis using transketolase.

    PubMed

    Lawrence, James; O'Sullivan, Brian; Lye, Gary J; Wohlgemuth, Roland; Szita, Nicolas

    2013-11-01

    Biocatalytic synthesis in continuous-flow microreactors is of increasing interest for the production of specialty chemicals. However, the yield of production achievable in these reactors can be limited by the adverse effects of high substrate concentration on the biocatalyst, including inhibition and denaturation. Fed-batch reactors have been developed in order to overcome this problem, but no continuous-flow solution exists. We present the design of a novel multi-input microfluidic reactor, capable of substrate feeding at multiple points, as a first step towards overcoming these problems in a continuous-flow setting. Using the transketolase-(TK) catalysed reaction of lithium hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose (ERY), we demonstrate the transposition of a fed-batch substrate feeding strategy to our microfluidic reactor. We obtained a 4.5-fold increase in output concentration and a 5-fold increase in throughput compared with a single input reactor.

  15. A bio-catalytic approach to aliphatic ketones.

    PubMed

    Xiong, Mingyong; Deng, Jin; Woodruff, Adam P; Zhu, Minshan; Zhou, Jun; Park, Sun Wook; Li, Hui; Fu, Yao; Zhang, Kechun

    2012-01-01

    Depleting oil reserves and growing environmental concerns have necessitated the development of sustainable processes to fuels and chemicals. Here we have developed a general metabolic platform in E. coli to biosynthesize carboxylic acids. By engineering selectivity of 2-ketoacid decarboxylases and screening for promiscuous aldehyde dehydrogenases, synthetic pathways were constructed to produce both C5 and C6 acids. In particular, the production of isovaleric acid reached 32 g/L (0.22 g/g glucose yield), which is 58% of the theoretical yield. Furthermore, we have developed solid base catalysts to efficiently ketonize the bio-derived carboxylic acids such as isovaleric acid and isocaproic acid into high volume industrial ketones: methyl isobutyl ketone (MIBK, yield 84%), diisobutyl ketone (DIBK, yield 66%) and methyl isoamyl ketone (MIAK, yield 81%). This hybrid "Bio-Catalytic conversion" approach provides a general strategy to manufacture aliphatic ketones, and represents an alternate route to expanding the repertoire of renewable chemicals.

  16. Experimental determination of thermodynamic equilibrium in biocatalytic transamination.

    PubMed

    Tufvesson, Pär; Jensen, Jacob S; Kroutil, Wolfgang; Woodley, John M

    2012-08-01

    The equilibrium constant is a critical parameter for making rational design choices in biocatalytic transamination for the synthesis of chiral amines. However, very few reports are available in the scientific literature determining the equilibrium constant (K) for the transamination of ketones. Various methods for determining (or estimating) equilibrium have previously been suggested, both experimental as well as computational (based on group contribution methods). However, none of these were found suitable for determining the equilibrium constant for the transamination of ketones. Therefore, in this communication we suggest a simple experimental methodology which we hope will stimulate more accurate determination of thermodynamic equilibria when reporting the results of transaminase-catalyzed reactions in order to increase understanding of the relationship between substrate and product molecular structure on reaction thermodynamics.

  17. Lipase-immobilized biocatalytic membranes for biodiesel production.

    PubMed

    Kuo, Chia-Hung; Peng, Li-Ting; Kan, Shu-Chen; Liu, Yung-Chuan; Shieh, Chwen-Jen

    2013-10-01

    Microbial lipase from Candida rugosa (Amano AY-30) has good transesterification activity and can be used for biodiesel production. In this study, polyvinylidene fluoride (PVDF) membrane was grafted with 1,4-diaminobutane and activated by glutaraldehyde for C. rugosa lipase immobilization. After immobilization, the biocatalytic membrane was used for producing biodiesel from soybean oil and methanol via transesterification. Response Surface Methodology (RSM) in combination with a 5-level-5-factor central composite rotatable design (CCRD) was employed to evaluate the effects of reaction time, reaction temperature, enzyme amount, substrate molar ratio and water content on the yield of soybean oil methyl ester. By ridge max analysis, the predicted and experimental yields under the optimum synthesis conditions were 97% and 95%, respectively. The lipase-immobilized PVDF membrane showed good reuse ability for biodiesel production, enabling operation for at least 165 h during five reuses of the batch, without significant loss of activity. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Biocatalytic Asymmetric Phosphorylation Catalyzed by Recombinant Glycerate-2-Kinase.

    PubMed

    Hardt, Norman; Kinfu, Birhanu M; Chow, Jennifer; Schoenenberger, Bernhard; Streit, Wolfgang R; Obkircher, Markus; Wohlgemuth, Roland

    2017-08-04

    The efficient synthesis of pure d-glycerate-2-phosphate is of great interest due to its importance as an enzyme substrate and metabolite. Therefore, we investigated a straightforward one-step biocatalytic phosphorylation of glyceric acid. Glycerate-2-kinase from Thermotoga maritima was expressed in Escherichia coli, allowing easy purification. The selective glycerate-2-kinase-catalyzed phosphorylation was followed by (31) P NMR and showed excellent enantioselectivity towards phosphorylation of the d-enantiomer of glyceric acid. This straightforward phosphorylation reaction and subsequent product isolation enabled the preparation of enantiomerically pure d-glycerate 2-phosphate. This phosphorylation reaction, using recombinant glycerate-2-kinase, yielded d-glycerate 2-phosphate in fewer reaction steps and with higher purity than chemical routes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2013-07-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  20. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann [Agoura Hills, CA

    2011-11-29

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  1. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2015-09-22

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  2. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2016-02-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  3. Rh(III)-Catalyzed Carbocyclization of 3-(Indolin-1-yl)-3-oxopropanenitriles with Alkynes and Alkenes through C-H Activation.

    PubMed

    Zhou, Tao; Wang, Yanwei; Li, Bin; Wang, Baiquan

    2016-10-07

    Rh(III)-catalyzed carbocyclization reactions of 3-(indolin-1-yl)-3-oxopropanenitriles with alkynes and alkenes have been developed to form 1,7-fused indolines through C-H activation. These reactions have a broad range of substrates and high yields. Unsymmetrical aryl-alkyl substituted alkynes proceeded smoothly with high regioselectivity. Electron-rich alkynes could undergo further oxidative coupling reaction to form polycyclic compounds. For alkenes, 1,2-dihydro-4H-pyrrolo[3,2,1-ij]quinolin-4-ones were formed via C(sp(2))-H bond alkenylation and C(sp(2))-H, C(sp(3))-H oxidative coupling reactions.

  4. Evidence for Alkene cis-Aminocupration, an Aminooxygenation Case Study: Kinetics, EPR Spectroscopy, and DFT Calculations

    PubMed Central

    Paderes, Monissa C.; Belding, Lee; Fanovic, Branden; Dudding, Travis; Keister, Jerome B.

    2012-01-01

    Alkene difunctionalization reactions are important in organic synthesis. We have recently shown that copper(II) complexes can promote and catalyze intramolecular alkene aminooxygenation, carboamination, and diamination reactions. In this contribution, we report a combined experimental and theoretical examination of the mechanism of the copper(II)-promoted olefin aminooxygenation reaction. Kinetics experiments revealed a mechanistic pathway involving an equilibrium reaction between a copper(II) carboxylate complex and the γ-alkenyl sulfonamide substrate and a rate-limiting intramolecular cis-addition of N–Cu across the olefin. Kinetic isotope effect studies support that the cis-aminocupration is the rate-determining step. UV/Vis spectra support a role for the base in the break-up of copper(II) carboxylate dimer to monomeric species. Electron paramagnetic resonance (EPR) spectra provide evidence for a kinetically competent N–Cu intermediate with a CuII oxidation state. Due to the highly similar stereochemical and reactivity trends among the CuII-promoted and catalyzed alkene difunctionalization reactions we have developed, the cis-aminocupration mechanism can reasonably be generalized across the reaction class. The methods and findings disclosed in this report should also prove valuable to the mechanism analysis and optimization of other copper(-II) carboxylate promoted reactions, especially those that take place in aprotic organic solvents. PMID:22237868

  5. Kinetics and mechanism of the oxidation of alkenes and silanes by hydrogen peroxide catalyzed by methylrhenium trioxide (MTO) and a novel application of electrospray mass spectrometry to study the hydrolysis of MTO

    SciTech Connect

    Tan, Haisong

    1999-11-08

    Conjugated dienes were oxidized by hydrogen peroxide with methylrhenium trioxide (MTO) as catalyst. Methylrhenium bis-peroxide was the major reactive catalyst present. Hydroxyalkenes and trisubstituted silane were also tested. Mechanisms for each of these reactions are presented.

  6. Radical product yields from the ozonolysis of short chain alkenes under atmospheric boundary layer conditions.

    PubMed

    Alam, Mohammed S; Rickard, Andrew R; Camredon, Marie; Wyche, Kevin P; Carr, Timo; Hornsby, Karen E; Monks, Paul S; Bloss, William J

    2013-11-27

    The gas-phase reaction of ozone with unsaturated volatile organic compounds (VOCs), alkenes, is an important source of the critical atmospheric oxidant OH, especially at night when other photolytic radical initiation routes cannot occur. Alkene ozonolysis is also known to directly form HO2 radicals, which may be readily converted to OH through reaction with NO, but whose formation is poorly understood. We report a study of the radical (OH, HO2, and RO2) production from a series of small alkenes (propene, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, 2,3-dimethyl-2-butene (tetramethyl ethene, TME), and isoprene). Experiments were performed in the European Photoreactor (EUPHORE) atmospheric simulation chamber, with OH and HO2 levels directly measured by laser-induced fluorescence (LIF) and HO2 + ΣRO2 levels measured by peroxy-radical chemical amplification (PERCA). OH yields were found to be in good agreement with the majority of previous studies performed under comparable conditions (atmospheric pressure, long time scales) using tracer and scavenger approaches. HO2 yields ranged from 4% (trans-2-butene) to 34% (2-methylpropene), lower than previous experimental determinations. Increasing humidity further reduced the HO2 yields obtained, by typically 50% for an RH increase from 0.5 to 30%, suggesting that HOx production from alkene ozonolysis may be lower than current models suggest under (humid) ambient atmospheric boundary layer conditions. The mechanistic origin of the OH and HO2 production observed is discussed in the context of previous experimental and theoretical studies.

  7. Asymmetric synthesis from terminal alkenes by cascades of diboration and cross-coupling.

    PubMed

    Mlynarski, Scott N; Schuster, Christopher H; Morken, James P

    2014-01-16

    Terminal, monosubstituted alkenes are ideal prospective starting materials for organic synthesis because they are manufactured on very large scales and can be functionalized via a broad range of chemical transformations. Alkenes also have the attractive feature of being stable in the presence of many acids, bases, oxidants and reductants. In spite of these attributes, relatively few catalytic enantioselective transformations have been developed that transform aliphatic α-olefins into chiral products with an enantiomeric excess greater then 90 per cent. With the exception of site-controlled isotactic polymerization of α-olefins, none of these catalytic enantioselective processes results in chain-extending carbon-carbon bond formation to the terminal carbon. Here we describe a strategy that directly addresses this gap in synthetic methodology, and present a single-flask, catalytic enantioselective conversion of terminal alkenes into a number of chiral products. These reactions are facilitated by a neighbouring functional group that accelerates palladium-catalysed cross-coupling of 1,2-bis(boronates) relative to non-functionalized alkyl boronate analogues. In tandem with enantioselective diboration, this reactivity feature transforms alkene starting materials into a diverse array of chiral products. We note that the tandem diboration/cross-coupling reaction generally provides products in high yield and high selectivity (>95:5 enantiomer ratio), uses low loadings (1-2 mol per cent) of commercially available catalysts and reagents, offers an expansive substrate scope, and can address a broad range of alcohol and amine synthesis targets, many of which cannot be easily addressed with current technology.

  8. Asymmetric synthesis from terminal alkenes by diboration/cross-coupling cascades

    PubMed Central

    Mlynarski, Scott N.; Schuster, Christopher H.; Morken, James P.

    2013-01-01

    Amongst prospective starting materials for organic synthesis, terminal (monosubstituted) alkenes are ideal. In the form of α-olefins, they are manufactured on enormous scale and they are the core product features from many organic chemical reactions. While their latent reactivity can easily enable hydrocarbon chain extension, alkenes also have the attractive feature of being stable in the presence of many acids, bases, oxidants and reductants. In spite of these impressive attributes, relatively few catalytic enantioselective transformations have been developed that transform aliphatic α-olefins in >90% ee and, with the exception of site-controlled isotactic polymerization of α-olefins,1 none of these processes result in chain-extending C-C bond formation to the terminal carbon.2, 3, 4, 5, 6 Herein, we describe a strategy that directly addresses this gap in synthetic methodology and present a single-flask catalytic enantioselective conversion of terminal alkenes into a range of chiral products. These reactions are enabled by an unusual neighboring group participation effect that accelerates Pd-catalyzed cross-coupling of 1,2-bis(boronates) relative to nonfunctionalized alkyl boronate analogs. In tandem with enantioselective diboration, this reactivity feature connects abundant alkene starting materials to a diverse array of chiral products. Importantly with respect to synthesis utility, the tandem diboration/cross-coupling reaction (DCC reaction) generally provides products in high yield and high selectivity (>95:5 enantiomer ratio), employs low loadings (1–2 mol %) of commercially available catalysts and reagents, it offers an expansive substrate scope, and can address a broad range of alcohol and amine synthesis targets, many of which cannot be easily addressed with current technology. PMID:24352229

  9. Asymmetric synthesis from terminal alkenes by cascades of diboration and cross-coupling

    NASA Astrophysics Data System (ADS)

    Mlynarski, Scott N.; Schuster, Christopher H.; Morken, James P.

    2014-01-01

    Terminal, monosubstituted alkenes are ideal prospective starting materials for organic synthesis because they are manufactured on very large scales and can be functionalized via a broad range of chemical transformations. Alkenes also have the attractive feature of being stable in the presence of many acids, bases, oxidants and reductants. In spite of these attributes, relatively few catalytic enantioselective transformations have been developed that transform aliphatic α-olefins into chiral products with an enantiomeric excess greater then 90 per cent. With the exception of site-controlled isotactic polymerization of α-olefins, none of these catalytic enantioselective processes results in chain-extending carbon-carbon bond formation to the terminal carbon. Here we describe a strategy that directly addresses this gap in synthetic methodology, and present a single-flask, catalytic enantioselective conversion of terminal alkenes into a number of chiral products. These reactions are facilitated by a neighbouring functional group that accelerates palladium-catalysed cross-coupling of 1,2-bis(boronates) relative to non-functionalized alkyl boronate analogues. In tandem with enantioselective diboration, this reactivity feature transforms alkene starting materials into a diverse array of chiral products. We note that the tandem diboration/cross-coupling reaction generally provides products in high yield and high selectivity (>95:5 enantiomer ratio), uses low loadings (1-2 mol per cent) of commercially available catalysts and reagents, offers an expansive substrate scope, and can address a broad range of alcohol and amine synthesis targets, many of which cannot be easily addressed with current technology.

  10. Nickel-Catalyzed Allylic Substitution of Simple Alkenes

    PubMed Central

    Matsubara, Ryosuke; Jamison, Timothy F.

    2011-01-01

    This report describes a nickel-catalyzed allylic substitution process of simple alkenes whereby an important structural motif, a 1,4-diene, was prepared. A key for this success is the use of an appropriate Ni-phosphine complex and a stoichiometric amount of silyl triflate. Reactions of 1-alkyl-substituted alkenes consistently provided 1,1-disubstituted alkenes with high selectivity. Insight into the reaction mechanism as well as miscellaneous application of the developed catalytic process is also documented. PMID:21387565

  11. Two-Input Enzymatic Logic Gates Made Sigmoid by Modifications of the Biocatalytic Reaction Cascades

    SciTech Connect

    Zavalov, Oleksandr; Bocharova, Vera; Halamek, Jan; Halamkova, Lenka; Korkmaz, Sevim; Arugula, Mary; Chinnapareddy, Soujanya; Katz, Evgeny; Privman, Vladimir

    2012-01-01

    Computing based on biochemical processes is a newest rapidly developing field of unconventional information and signal processing. In this paper we present results of our research in the field of biochemical computing and summarize the obtained numerical and experimental data for implementations of the standard two-input OR and AND gates with double-sigmoid shape of the output signal. This form of response was obtained as a function of the two inputs in each of the realized biochemical systems. The enzymatic gate processes in the first system were activated with two chemical inputs and resulted in optically detected chromogen oxidation, which happens when either one or both of the inputs are present. In this case, the biochemical system is functioning as the OR gate. We demonstrate that the addition of a filtering biocatalytic process leads to a considerable reduction of the noise transmission factor and the resulting gate response has sigmoid shape in both inputs. The second system was developed for functioning as an AND gate, where the output signal was activated only by a simultaneous action of two enzymatic biomarkers. This response can be used as an indicator of liver damage, but only if both of these of the inputs are present at their elevated, pathophysiological values of concentrations. A kinetic numerical model was developed and used to estimate the range of parameters for which the experimentally realized logic gate is close to optimal. We also analyzed the system to evaluate its noise-handling properties.

  12. Enzyme-Modified Particles for Selective Biocatalytic Hydrogenation by Hydrogen-Driven NADH Recycling

    PubMed Central

    Reeve, Holly A; Lauterbach, Lars; Lenz, Oliver; Vincent, Kylie A

    2015-01-01

    We describe a new approach to selective H2-driven hydrogenation that exploits a sequence of enzymes immobilised on carbon particles. We used a catalyst system that comprised alcohol dehydrogenase, hydrogenase and an NAD+ reductase on carbon black to demonstrate a greater than 98 % conversion of acetophenone to phenylethanol. Oxidation of H2 by the hydrogenase provides electrons through the carbon for NAD+ reduction to recycle the NADH cofactor required by the alcohol dehydrogenase. This biocatalytic system operates over the pH range 6–8 or in un-buffered water, and can function at low concentrations of the cofactor (10 μm NAD+) and at H2 partial pressures below 1 bar. Total turnover numbers >130 000 during acetophenone reduction indicate high enzyme stability, and the immobilised enzymes can be recovered by a simple centrifugation step and re-used several times. This offers a route to convenient, atom-efficient operation of NADH-dependent oxidoreductases for selective hydrogenation catalysis. PMID:26613009

  13. Synthesis of trans-disubstituted alkenes by cobalt-catalyzed reductive coupling of terminal alkynes with activated alkenes.

    PubMed

    Mannathan, Subramaniyan; Cheng, Chien-Hong

    2012-09-10

    A cobalt-catalyzed reductive coupling of terminal alkynes, RC≡CH, with activated alkenes, R'CH=CH(2), in the presence of zinc and water to give functionalized trans-disubstituted alkenes, RCH=CHCH(2)CH(2)R', is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl(2)/P(OMe)(3)/Zn catalyst system to afford 1,2-trans-disubstituted alkenes with high regio- and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl(2)/P(OPh)(3)/Zn system providing a mixture of 1,2-trans- and 1,1-disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3-enynes and acetylene gas with alkenes. Furthermore, a phosphine-free cobalt-catalyzed reductive coupling of terminal alkynes with enones, affording 1,2-trans-disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air-stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Asymmetric Reduction of Activated Alkenes by Pentaerythritol Tetranitrate Reductase: Specificity and Control of Stereochemical Outcome by Reaction Optimisation

    PubMed Central

    Fryszkowska, Anna; Toogood, Helen; Sakuma, Michiyo; Gardiner, John M.; Stephens, Gill M.; Scrutton, Nigel S.

    2009-01-01

    We show that pentaerythritol tetranitrate reductase (PETNR), a member of the ‘ene’ reductase old yellow enzyme family, catalyses the asymmetric reduction of a variety of industrially relevant activated α,β-unsaturated alkenes including enones, enals, maleimides and nitroalkenes. We have rationalised the broad substrate specificity and stereochemical outcome of these reductions by reference to molecular models of enzyme-substrate complexes based on the crystal complex of the PETNR with 2-cyclohexenone 4a. The optical purity of products is variable (49–99% ee), depending on the substrate type and nature of substituents. Generally, high enantioselectivity was observed for reaction products with stereogenic centres at Cβ (>99% ee). However, for the substrates existing in two isomeric forms (e.g., citral 11a or nitroalkenes 18–19a), an enantiodivergent course of the reduction of E/Z-forms may lead to lower enantiopurities of the products. We also demonstrate that the poor optical purity obtained for products with stereogenic centres at Cα is due to non-enzymatic racemisation. In reactions with ketoisophorone 3a we show that product racemisation is prevented through reaction optimisation, specifically by shortening reaction time and through control of solution pH. We suggest this as a general strategy for improved recovery of optically pure products with other biocatalytic conversions where there is potential for product racemisation. PMID:20396613

  15. Novel anticancer alkene lactone from Persea americana.

    PubMed

    Falodun, Abiodun; Engel, Nadja; Kragl, Udo; Nebe, Barbara; Langer, Peter

    2013-06-01

    Persea americana Mill (Lauraceae) root bark is used in ethnomedicine for a variety of diseases including cancer. To isolate and characterize the chemical constituent in P. americana, and also to determine the anticancer property of a new alkene lactone from the root bark of P. americana. The MCF-7 cells were treated with different concentrations of the pure compound for 48 h. The percentage of cells in the various phases, online monitoring of metabolic changes and integrin receptor expression determined by flow cytometry. One novel alkene lactone (4-hydroxy-5-methylene-3-undecyclidenedihydrofuran-2 (3H)-one) (1) was isolated and characterized using 1D-NMR, 2D-NMR, infrared, UV and MS. At a concentration of 10 µg/mL, significant reduction of proliferation of MCF-7 was induced while MCF-12 A cell was significantly stimulated by 10 µg/mL. The IC50 value for MCF-7 cells is 20.48 µg/mL. Lower concentration of 1 harbor no significant effect on either MCF-7 or MCF-12A. The apoptotic rates of MCF-7 cells were increased significantly. At the final concentration 10 µg/mL, up to 80% of all breast cancer cells were dead. On the non-tumorigenic cell line MCF-12A, the same concentrations (1 and 10 µg/mL) of compound 1 caused significant enhanced apoptotic rates. A total of 1 µg/mL of 1 caused a decrease of α4-, α6-, β1- and β3-integrin expression. The compound caused a stimulatory effect on non-tumorigenic MCF-12A cells with respect to cell adhesion while tumorigenic MCF-7 cells detached continuously. This is the first report on the anticancer effects of this class of compound.

  16. Rhodium-Catalyzed Dehydrogenative Borylation of Cyclic Alkenes

    PubMed Central

    Kondoh, Azusa; Jamison, Timothy F.

    2010-01-01

    A rhodium-catalyzed dehydrogenative borylation of cyclic alkenes is described. This reaction provides direct access to cyclic 1-alkenylboronic acid pinacol esters, useful intermediates in organic synthesis. Suzuki-Miyaura cross-coupling applications are also presented. PMID:20107646

  17. Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities.

    PubMed

    Cresswell, Alexander J; Eey, Stanley T-C; Denmark, Scott E

    2015-12-21

    Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations of alkenes, the related dihalogenation of olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, the growing number of complex natural products bearing halogen atoms at stereogenic centers has underscored this critical gap in the synthetic chemist's arsenal. This Review highlights the selectivity challenges inherent in the design of enantioselective dihalogenation processes, and formulates a mechanism-based classification of alkene dihalogenations, including those that may circumvent the "classical" haliranium (or alkene-dihalogen π-complex) intermediates. A variety of metal and main group halide reagents that have been used for the dichlorination or dibromination of alkenes are discussed, and the proposed mechanisms of these transformations are critically evaluated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Alkene dihydroxylation with malonoyl peroxides: catalysis using fluorinated alcohols.

    PubMed

    Picon, Sylvain; Rawling, Michael; Campbell, Matthew; Tomkinson, Nicholas C O

    2012-12-21

    The effect of fluorinated alcohols on the dihydroxylation of alkenes using cyclopropyl malonoyl peroxide is described. Addition of perfluoro-tert-butyl alcohol to a toluene solution of alkene and peroxide increases the rate of product formation and the stereoselectivity observed, providing a simple and effective method for acceleration of this important class of reaction. Basic hydrolysis of the crude reaction mixture provides access to syn-diols in high yield and stereoselectivity.

  19. Hydroaminations of alkenes: a radical, revised, and expanded version.

    PubMed

    Villa, Matteo; Jacobi von Wangelin, Axel

    2015-10-05

    Radical changes: The applicability of alkene hydroamination has recently been significantly expanded by the development of radical variants that are based on initial hydrogen atom transfer to the alkene. This Highlight assesses the current state of the art, focusing on an iron-catalyzed reaction that utilizes stable nitroarenes as the electrophilic N component and is based on the dual catalytic activation of both starting materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Room Temperature Hydrosilylation of Silicon Nanocrystals with Bifunctional Terminal Alkenes

    PubMed Central

    Yu, Yixuan; Hessel, Colin M.; Bogart, Timothy; Panthani, Matthew G.; Rasch, Michael R.; Korgel, Brian A.

    2013-01-01

    H-terminated Si nanocrystals undergo room temperature hydrosilylation with bifunctional alkenes with distal polar moieties—ethyl-, methyl-ester or carboxylic acids—without the aid of light or added catalyst. The passivated Si nanocrystals exhibit bright photoluminescence (PL) and disperse in polar solvents, including water. We propose a reaction mechanism in which ester or carboxylic acid groups facilitate direct nucleophilic attack of the highly curved Si surface of the nanocrystals by the alkene. PMID:23312033

  1. Ligand-Controlled Regiodivergent Copper-Catalyzed Alkylboration of Alkenes.

    PubMed

    Su, Wei; Gong, Tian-Jun; Lu, Xi; Xu, Meng-Yu; Yu, Chu-Guo; Xu, Zheng-Yang; Yu, Hai-Zhu; Xiao, Bin; Fu, Yao

    2015-10-26

    A novel copper-catalyzed regiodivergent alkylboration of alkenes with bis(pinacolato)diboron and alkyl halides has been developed. The regioselectivity of the alkylboration was controlled by subtle differences in the ligand structure. The reaction thus enables the practical, regiodivergent synthesis of two different alkyl boronic esters with complex structures from a single alkene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enantio- and Regioselective CuH-Catalyzed Hydroamination of Alkenes

    PubMed Central

    Zhu, Shaolin; Niljianskul, Nootaree; Buchwald, Stephen L.

    2013-01-01

    A highly enantio- and regioselective copper-catalyzed hydroamination reaction of alkenes has been developed using diethoxy(methyl)silane (DEMS) and esters of hydroxylamines. The process tolerates a wide variety of substituted styrenes, including trans-, cis-, and β,β-disubstituted styrenes to yield α–branched amines. In addition, aliphatic alkenes coupled to generate exclusively the anti-Markovnikov hydroamination products. PMID:24106781

  3. Osmium(III) and osmium(V) complexes bearing a macrocyclic ligand: a simple and efficient catalytic system for cis-dihydroxylation of alkenes with hydrogen peroxide.

    PubMed

    Sugimoto, Hideki; Ashikari, Kenji; Itoh, Shinobu

    2013-09-01

    A simple protocol that uses [Os(III)(OH)(H2O)(L-N4Me2)](PF6)2 (1; L-N4Me2 = N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane) as a catalyst and H2O2 as a terminal oxidant for efficient cis-1,2-dihydroxylation of alkenes is presented. Unfunctionalized (or aliphatic) alkenes and alkenes/styrenes containing electron-withdrawing groups are selectively oxidized to the corresponding vicinal diols in good to excellent yields (46-99 %). In the catalytic reactions, the stoichiometry of alkene:H2O2 is 1:1, and thus the oxidant efficiency is very high. For the dihydroxylation of cyclohexene, the catalytic amount of 1 can be reduced to 0.01 mol % to achieve a very high turnover number of 5500. The active oxidant is identified as the Os(V)(O)(OH) species (2), which is formed via the hydroperoxide adduct, an Os(III)(OOH) species. The active oxidant 2 is successfully isolated and crystallographically characterized. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Regio- and stereoselective synthesis of pregnane-fused isoxazolines by nitril-oxide/alkene 1,3-dipolar cycloaddition and an evaluation of their cell-growth inhibitory effect in vitro

    NASA Astrophysics Data System (ADS)

    Mótyán, Gergő; Baji, Ádám; Zupkó, István; Frank, Éva

    2016-04-01

    Efficient syntheses of some pregnane-fused isoxazolines from 16-dehydropregnenolone acetate with different arylnitrile oxides were carried out by 1,3-dipolar cycloadditions. The intermolecular ring-closures occurred in a highly regio- and stereoselective manner permitting the formation of a single 16α,17α-condensed diastereomer in which the O terminus of the nitrile oxide dipole is attached to C-17 of the sterane core. The conversions were found to be affected significantly by the electronic character of the substituents on the aromatic moiety of the 1,3-dipoles. Deacetylation of the primary products resulted in the corresponding 3β-OH analogs. All of the synthesized compounds were subjected to in vitro pharmacological studies for the determination of their antiproliferative effects on four breast cancer cell lines (MCF7, T47D, MDA-MB-231 and MDA-MB-361).

  5. Palladium-catalyzed selective acyloxylation using sodium perborate as oxidant.

    PubMed

    Pilarski, Lukasz T; Janson, Pär G; Szabó, Kálmán J

    2011-03-04

    Sodium perborate (SPB), a principal component of washing powders, was employed as an inexpensive and eco-friendly oxidant in the palladium-catalyzed C-H acyloxylation of alkenes in excellent regio- and stereochemistry. The reactions used anhydrides as acyloxy sources. The method applies to both terminal and internal alkenes, and even benzylic C-H oxidation.

  6. Stability of prostacyclin analogues: an unusual lack of reactivity in acid-catalyzed alkene hydration.

    PubMed

    Magill, A; O'Yang, C; Powell, M F

    1988-04-01

    Prostacyclin analogue 5 undergoes specific acid-catalyzed hydration (kH+ = 1.9 x 10(-7)M-1 sec-1 at 25 degrees C) and a pH-independent oxidation reaction (k0 = 1.2 x 10(-10) sec-1 at 25 degrees C) above pH approximately 5. The hydration reaction for 5 is much slower than for other structurally similar exocyclic alkenes, even though the rate-determining step is proton transfer. This slowness of reaction and an analysis of the pH-rate profile show that 5 does not exhibit significant intramolecular general acid catalysis, as does prostacyclin.

  7. How Do Phosphinates React with Unactivated Alkenes Under Organic Photocatalyzed Conditions? Substrate Scope and Mechanistic Insights.

    PubMed

    Fausti, Giovanni; Morlet-Savary, Fabrice; Lalevée, Jacques; Gaumont, Annie-Claude; Lakhdar, Sami

    2017-02-10

    The first visible-light-mediated, metal-free hydrophosphinylation of unactivated alkenes with ethyl and butyl phosphinates is described. The reaction works with a low catalyst loading of 9-mesityl-10-methylacridinium perchlorate (Fukuzumi photocatalyst, 0.5 mol %) in the presence of diphenyliodonium triflate as oxidant. The reaction proceeds smoothly and covers a broad scope of substrates. Detailed mechanistic investigations, including EPR spectroscopy, fluorescence and steady-state photolysis, allowed the mechanism of this photoreaction to be rationalized. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Heterocycle synthesis by copper facilitated addition of heteroatoms to alkenes, alkynes and arenes.

    PubMed

    Chemler, Sherry R; Fuller, Peter H

    2007-07-01

    The de novo synthesis of small organic heterocyclic molecules has benefited from recent protocols for copper-facilitated additions of heteroatoms to alkenes, alkynes and arenes. This tutorial review summarizes a number of these recent contributions. Copper salts can facilitate bond formations due to their ability to serve as Lewis acids, oxidizing agents and transition metal catalysts. The current understanding of the mechanisms of these reactions is presented. This review should be of interest to chemists involved in the synthesis of heterocycles and those investigating transition metal facilitated reactions.

  9. Manganese(IV)-mediated hydroperoxyarylation of alkenes with aryl hydrazines and dioxygen from air.

    PubMed

    Kindt, Stephanie; Jasch, Hannelore; Heinrich, Markus R

    2014-05-19

    We report a new carbooxygenation-type version of the Meerwein arylation in which the introduction of oxygen is achieved by using dioxygen from the air. In this way, hydroperoxides were obtained from activated as well as non-activated alkenes by oxidizing aryl hydrazines with manganese dioxide. The best results were obtained with α-substituted acrylates. Importantly, the aryl hydrazine has to be added slowly to the reaction mixture to allow sufficient uptake of dioxygen from the air. Competition and labeling experiments revealed hydroperoxyl radicals as novel oxygen-centered radical scavengers.

  10. Oxidative Reactions with Nonaqueous Enzymes

    SciTech Connect

    Jonathan S. Dordick; Douglas Clark; Brian H Davison; Alexander Klibanov

    2001-12-30

    The objective of this work is to demonstrate a proof-of-concept of enzymatic oxidative processing in nonaqueous media using alkene epoxidation and phenolic polymerization as relevant targets. This project will provide both the fundamental and applied investigations necessary to initiate the implementation of oxidative biocatalysts as commercially relevant alternatives to chemical processing in general, and to phenolic polymerizations and alkene epoxidation specifically. Thus, this work will address the Bioprocessing Solicitation Area to: (1) makes major improvements to phenolic polymerization and alkene epoxidation technologies; (2) is expected to be cost competitive with competing conventional processes; and (3) produces higher yields with less waste.

  11. NMP and O2 as Radical Initiator: Trifluoromethylation of Alkenes to Tertiary β-Trifluoromethyl Alcohols at Room Temperature.

    PubMed

    Liu, Chao; Lu, Qingquan; Huang, Zhiyuan; Zhang, Jian; Liao, Fan; Peng, Pan; Lei, Aiwen

    2015-12-18

    A novel strategy was developed to trigger ·CF3 by using in situ generated peroxide in NMP under O2 or air as the radical initiator. Radical trifluoromethylation of alkenes was achieved toward tertiary β-trifluoromethyl alcohols. Various tertiary β-trifluoromethyl alcohols can be synthesized in good yields without extra oxidants or transition metal catalysts. Preliminary mechanistic investigation revealed that O2 diffusion can influence the reaction rate.

  12. Copper Nitrate Mediated Regioselective [2+2+1] Cyclization of Alkynes with Alkenes: A Cascade Approach to Δ(2)-Isoxazolines.

    PubMed

    Gao, Mingchun; Li, Yingying; Gan, Yuansheng; Xu, Bin

    2015-07-20

    An efficient method for the regioselective synthesis of pharmacologically relevant polysubstituted Δ(2)-isoxazolines is based on the copper-mediated direct transformation of simple terminal alkynes and alkenes. The overall process involves the formation of four chemical bonds with inexpensive and readily available copper nitrate trihydrate as a novel precursor of nitrile oxides. The reaction can be easily handled and proceeds under mild conditions.

  13. Epoxidation of Short-Chain Alkenes by Resting-Cell Suspensions of Propane-Grown Bacteria

    PubMed Central

    Hou, Ching T.; Patel, Ramesh; Laskin, Allen I.; Barnabe, Nancy; Barist, Irene

    1983-01-01

    Sixteen new cultures of propane-utilizing bacteria were isolated from lake water from Warinanco Park, Linden, N.J. and from lake and soil samples from Bayway Refinery, Linden, N.J. In addition, 19 known cultures obtained from culture collections were also found to be able to grow on propane as the sole carbon and energy source. In addition to their ability to oxidize n-alkanes, resting-cell suspensions of both new cultures and known cultures grown on propane oxidize short-chain alkenes to their corresponding 1,2-epoxides. Among the substrate alkenes, propylene was oxidized at the highest rate. In contrast to the case with methylotrophic bacteria, the product epoxides are further metabolized. Propane and other gaseous n-alkanes inhibit the epoxidation of propylene. The optimum conditions for in vivo epoxidation are described. Results from inhibition studies indicate that a propane monooxygenase system catalyzes both the epoxidation and hydroxylation reactions. Experiments with cell-free extracts show that both hydroxylation and epoxidation activities are located in the soluble fraction obtained after 80,000 × g centrifugation. PMID:16346338

  14. Transition-metal-free Chemoselective Oxidative C-C Coupling of the sp(3) C-H Bond of Oxindoles with Arenes and Addition to Alkene: Synthesis of 3-Aryl Oxindoles, and Benzofuro- and Indoloindoles.

    PubMed

    Sattar, Moh; Rathore, Vandana; Prasad, Ch Durga; Kumar, Sangit

    2017-04-04

    A transition-metal (TM)-free and halogen-free NaOtBu-mediated oxidative cross-coupling between the sp(3) C-H bond of oxindoles and sp(2) C-H bond of nitroarenes has been developed to access 3-aryl substituted and 3,3-aryldisubstituted oxindoles in DMSO at room temperature in a short time. Interestingly, the sp(3) C-H bond of oxindoles could also react with styrene under TM-free conditions for the practical synthesis of quaternary 3,3-disubstituted oxindoles. The synthesized 3-oxindoles have also been further transformed into advanced heterocycles, that is, benzofuroindoles, indoloindoles, and substituted indoles. Mechanistic experiments of the reaction suggests the formation of an anion intermediate from the sp(3) C-H bond of oxindole by tert-butoxide base in DMSO. The addition of nitrobenzene to the in-situ generated carbanion leads to the 3-(nitrophenyl)oxindolyl carbanion in DMSO which is subsequently oxidized to 3-(nitro-aryl) oxindole by DMSO.

  15. Iron- and Cobalt-Catalyzed Alkene Hydrogenation: Catalysis with Both Redox-Active and Strong Field Ligands.

    PubMed

    Chirik, Paul J

    2015-06-16

    The hydrogenation of alkenes is one of the most impactful reactions catalyzed by homogeneous transition metal complexes finding application in the pharmaceutical, agrochemical, and commodity chemical industries. For decades, catalyst technology has relied on precious metal catalysts supported by strong field ligands to enable highly predictable two-electron redox chemistry that constitutes key bond breaking and forming steps during turnover. Alternative catalysts based on earth abundant transition metals such as iron and cobalt not only offer potential environmental and economic advantages but also provide an opportunity to explore catalysis in a new chemical space. The kinetically and thermodynamically accessible oxidation and spin states may enable new mechanistic pathways, unique substrate scope, or altogether new reactivity. This Account describes my group's efforts over the past decade to develop iron and cobalt catalysts for alkene hydrogenation. Particular emphasis is devoted to the interplay of the electronic structure of the base metal compounds and their catalytic performance. First generation, aryl-substituted pyridine(diimine) iron dinitrogen catalysts exhibited high turnover frequencies at low catalyst loadings and hydrogen pressures for the hydrogenation of unactivated terminal and disubstituted alkenes. Exploration of structure-reactivity relationships established smaller aryl substituents and more electron donating ligands resulted in improved performance. Second generation iron and cobalt catalysts where the imine donors were replaced by N-heterocyclic carbenes resulted in dramatically improved activity and enabled hydrogenation of more challenging unactivated, tri- and tetrasubstituted alkenes. Optimized cobalt catalysts have been discovered that are among the most active homogeneous hydrogenation catalysts known. Synthesis of enantiopure, C1 symmetric pyridine(diimine) cobalt complexes have enabled rare examples of highly enantioselective

  16. Biocatalytic nerve agent detoxification in fire fighting foams.

    PubMed

    LeJeune, K E; Russell, A J

    1999-03-20

    Current events across the globe necessitate rapid technological advances to combat the epidemic of nerve agent chemical weapons. Biocatalysis has emerged as a viable tool in the detoxification of organophosphorus neurotoxins, such as the chemical weapons VX and sarin. Efficient detoxification of contaminated equipment, machinery, and soils are of principal concern. This study describes the incorporation of a biocatalyst (organophosphorus hydrolase, E.C. 3.1.8.1) into conventional formulations of fire fighting foam. The capacity of fire fighting foams to decrease volatilization of contained contaminants, increase surface wettability, and control the rate of enzyme delivery to large areas makes them useful vehicles for enzyme application at surfaces. The performance of enzyme containing foams has been shown to be not only reproducible but also predictable. An empirical model provides reasonable estimations for the amounts of achievable surface decontamination as a function of the important parameters of the system. Theoretical modeling illustrates that the enzyme-containing foam is capable of extracting agent from the surface and is catalytically active at the foam-surface interface and throughout the foam itself. Biocatalytic foam has proven to be an effective, "environmentally friendly" means of surface and soil decontamination.

  17. Biocatalytic potential of vanillin aminotransferase from Capsicum chinense

    PubMed Central

    2014-01-01

    Background The conversion of vanillin to vanillylamine is a key step in the biosynthetic route towards capsaicinoids in pungent cultivars of Capsicum sp. The reaction has previously been annotated to be catalysed by PAMT (putative aminotransferase; [GenBank: AAC78480.1, Swiss-Prot: O82521]), however, the enzyme has previously not been biochemically characterised in vitro. Results The biochemical activity of the transaminase was confirmed by direct measurement of the reaction with purified recombinant enzyme. The enzyme accepted pyruvate, and oxaloacetate but not 2-oxoglutarate as co-substrate, which is in accordance with other characterised transaminases from the plant kingdom. The enzyme was also able to convert (S)-1-phenylethylamine into acetophenone with high stereo-selectivity. Additionally, it was shown to be active at a broad pH range. Conclusions We suggest PAMT to be renamed to VAMT (vanillin aminotransferase, abbreviation used in this study) as formation of vanillin from vanillylamine could be demonstrated. Furthermore, due to high stereoselectivity and activity at physiological pH, VAMT is a suitable candidate for biocatalytic transamination in a recombinant whole-cell system. PMID:24712445

  18. Effectiveness Factors and Conversion in a Biocatalytic Membrane Reactor.

    PubMed

    Godongwana, Buntu

    2016-01-01

    Analytical expressions of the effectiveness factor of a biocatalytic membrane reactor, and its asymptote as the Thiele modulus becomes large, are presented. The evaluation of the effectiveness factor is based on the solution of the governing equations for solute transport in the two regions of the reactor, i.e. the lumen and the matrix (with the biofilm immobilized in the matrix). The lumen solution accounts for both axial diffusion and radial convective flow, while the matrix solution is based on Robin-type boundary conditions. The effectiveness factor is shown to be a function of the Thiele modulus, the partition coefficient, the Sherwood number, the Peclet number, and membrane thickness. Three regions of Thiele moduli are defined in the effectiveness factor graphs. These correspond with reaction rate limited, internal-diffusion limited, and external mass transfer limited solute transport. Radial convective flows were shown to only improve the effectiveness factor in the region of internal diffusion limitation. The assumption of first order kinetics is shown to be applicable only in the Thiele modulus regions of internal and external mass transfer limitation. An iteration scheme is also presented for estimating the effectiveness factor when the solute fractional conversion is known. The model is validated with experimental data from a membrane gradostat reactor immobilised with Phanerochaete chrysosporium for the production of lignin and manganese peroxidases. The developed model and experimental data allow for the determination of the Thiele modulus at which the effectiveness factor and fractional conversion are optimal.

  19. Effectiveness Factors and Conversion in a Biocatalytic Membrane Reactor

    PubMed Central

    Godongwana, Buntu

    2016-01-01

    Analytical expressions of the effectiveness factor of a biocatalytic membrane reactor, and its asymptote as the Thiele modulus becomes large, are presented. The evaluation of the effectiveness factor is based on the solution of the governing equations for solute transport in the two regions of the reactor, i.e. the lumen and the matrix (with the biofilm immobilized in the matrix). The lumen solution accounts for both axial diffusion and radial convective flow, while the matrix solution is based on Robin-type boundary conditions. The effectiveness factor is shown to be a function of the Thiele modulus, the partition coefficient, the Sherwood number, the Peclet number, and membrane thickness. Three regions of Thiele moduli are defined in the effectiveness factor graphs. These correspond with reaction rate limited, internal-diffusion limited, and external mass transfer limited solute transport. Radial convective flows were shown to only improve the effectiveness factor in the region of internal diffusion limitation. The assumption of first order kinetics is shown to be applicable only in the Thiele modulus regions of internal and external mass transfer limitation. An iteration scheme is also presented for estimating the effectiveness factor when the solute fractional conversion is known. The model is validated with experimental data from a membrane gradostat reactor immobilised with Phanerochaete chrysosporium for the production of lignin and manganese peroxidases. The developed model and experimental data allow for the determination of the Thiele modulus at which the effectiveness factor and fractional conversion are optimal. PMID:27104954

  20. Chitosan-based biocatalytic nanoparticles for pollutant removal from wastewater.

    PubMed

    Alarcón-Payán, Dulce A; Koyani, Rina D; Vazquez-Duhalt, Rafael

    2017-05-01

    Chitosan, a renewable biopolymer has the prospective applications in different fields due to its gelation capacity. Nanoconfiguration of chitosan through ionotropic gelation to encapsulate enzymatic activity offers numerous potential applications. In the present study, the preparation and characterization of chitosan nanoparticles loaded with versatile peroxidase are reported. Their performance in bioremediation process and the resistance enhancement against natural microbial biodegradation were studied. The average diameter of enzymatic nanoparticles was 120nm and showed a high enzyme loading capacity. The kinetic parameters of nanoparticles exhibited a slightly lower catalytic activity (kcat), similar affinity constant (Km) for hydrogen peroxide and higher Km value for the phenolic compound when compared with the free enzyme. The enzymatic nanoparticles showed higher thermostability and the same pH activity profile than those from free enzyme. Ten phenolic compounds, including pesticides, halogenated compounds, endocrine disruptors and antibacterials were transformed by the enzymatic nanoparticles. The transformation rate was lower than those obtained with free enzyme suggesting mass transfer limitations. But very importantly, the enzymatic nanoparticles showed a significant increase of the operational stability in real conditions of wastewater treatment process. Moreover, chemical modification of nanoparticles with different aldehydes still enhanced the operational stability of nanoparticulated enzymes. This enhancement of stability in real conditions and the potential use of biocatalytic nanoparticles in bioremediation processes are discussed.

  1. An Umpolung Approach to Alkene Carboamination: Palladium Catalyzed 1,2-Amino-Acylation, -Carboxylation, -Arylation, -Vinylation, and -Alkynylation.

    PubMed

    Faulkner, Adele; Scott, James S; Bower, John F

    2015-06-10

    Conventional approaches to Pd-catalyzed alkene 1,2-carboamination rely upon the combination of a nucleophilic nitrogen-based component and an internal C-based or external oxidant. In this study, we outline an umpolung approach, which is triggered by oxidative initiation at an electrophilic N-based component and employs "standard" organometallic nucleophiles to introduce the new carbon-based fragment. Specifically, oxidative addition of a Pd(0)-catalyst into the N-O bond of O-pentafluorobenzoyl oxime esters generates imino-Pd(II) intermediates, which undergo 5-exo cyclization with sterically diverse alkenes. The resultant alkyl-Pd(II) intermediates are intercepted by organometallic nucleophiles or alcohols, under carbonylative or noncarbonylative conditions, to provide 1,2-carboamination products. This approach provides, for the first time, a unified strategy for achieving alkene 1,2-amino-acylation, -carboxylation, -arylation, -vinylation, and -alkynylation. For carbonylative processes, orchestrated protodecarboxylation of the pentafluorobenzoate leaving group underpins reaction efficiency. This process is likely a key feature in related Narasaka-Heck cyclizations and accounts for the efficacy of O-pentafluorobenzoyl oxime esters in aza-Heck reactions of this type.

  2. One-pot synthesis of α,β-epoxy ketones through domino reaction between alkenes and aldehydes catalyzed by proline based chiral organocatalysts.

    PubMed

    Ashokkumar, Veeramanoharan; Siva, Ayyanar

    2017-03-22

    Proline based metal free organocatalysts were developed by using a new approach for the synthesis of epoxide derivatives through a domino reaction. This domino reaction (oxidative coupling) allows a direct access to epoxides from various alkenes and aldehydes through C-H functionalization and C-C/C-O bond formation. The catalytic efficiencies of the newly synthesized organocatalysts were also determined by domino reaction in the presence of various functional groups containing aldehyde and alkene derivatives with very good yields (up to 95%) and ee's (up to 99%).

  3. Perspectives for biocatalytic lignin utilization: cleaving 4-O-5 and Cα-Cβ bonds in dimeric lignin model compounds catalyzed by a promiscuous activity of tyrosinase.

    PubMed

    Min, Kyoungseon; Yum, Taewoo; Kim, Jiye; Woo, Han Min; Kim, Yunje; Sang, Byoung-In; Yoo, Young Je; Kim, Yong Hwan; Um, Youngsoon

    2017-01-01

    In the biorefinery utilizing lignocellulosic biomasses, lignin decomposition to value-added phenolic derivatives is a key issue, and recently biocatalytic delignification is emerging owing to its superior selectivity, low energy consumption, and unparalleled sustainability. However, besides heme-containing peroxidases and laccases, information about lignolytic biocatalysts is still limited till date. Herein, we report a promiscuous activity of tyrosinase which is closely associated with delignification requiring high redox potentials (>1.4 V vs. normal hydrogen electrode [NHE]). The promiscuous activity of tyrosinase not only oxidizes veratryl alcohol, a commonly used nonphenolic substrate for assaying ligninolytic activity, to veratraldehyde but also cleaves the 4-O-5 and Cα-Cβ bonds in 4-phenoxyphenol and guaiacyl glycerol-β-guaiacyl ether (GGE) that are dimeric lignin model compounds. Cyclic voltammograms additionally verified that the promiscuous activity oxidizes lignin-related high redox potential substrates. These results might be applicable for extending the versatility of tyrosinase toward biocatalytic delignification as well as suggesting a new perspective for sustainable lignin utilization. Furthermore, the results provide insight for exploring the previously unknown promiscuous activities of biocatalysts much more diverse than ever thought before, thereby innovatively expanding the applicable area of biocatalysis.

  4. OH radical formation from the gas-phase reaction of ozone with terminal alkenes and the relationship between structure and mechanism

    SciTech Connect

    Paulson, S.E.; Chung, M.Y.; Hasson, A.S.

    1999-10-14

    The reactions of ozone with alkenes have been shown recently to lead to the direct production of OH radicals in quantities that vary from 7 to 100% depending on the structure of the alkene. OH radicals are the most important oxidizing species in the lower atmosphere, and the OH-alkene reaction is a large source of new OH radicals, important in urban and rural air during both day and night. Evidence for OH formation comes both from low-pressure direct measurements and from tracer experiments at high pressure. With the goal of measuring OH formation yields with good precision, a small-ratio relative rate technique was developed. This method uses small amounts of fast-reacting aromatics and aliphatic ethers to trace OH formation yields. Here, the authors report OH formation yields for a series of terminal alkenes reacting with ozone. Measured OH yields were 0.29 {+-} 0.05, 0.24 {+-} 0.05, 0.18 {+-} 0.04, and 0.10 {+-} 0.03 for 1-butene, 1-pentene, 1-hexene, and 1-octene, respectively. For the methyl-substituted terminal alkenes methyl propene and 2-methyl-1-butene, OH yields were 0.72 {+-} 0.12 and 0.67 {+-} 0.12, respectively. The results are discussed both in terms of their atmospheric implications and the relationship between structure and OH formation.

  5. Determining the Impact of Ligand and Alkene Substituents on Bonding in Gold(I)-Alkene Complexes Supported by N-Heterocyclic Carbenes: A Computational Study.

    PubMed

    York, John T

    2016-08-04

    The nature of the gold(I)-alkene bond in [(NHC)Au(alkene)](+) complexes (where NHC is the N-heterocyclic carbene 1,3-bis(2,6-dimethylphenyl)imidazole-2-ylidine and its derivatives) has been studied using density functional theory. By utilization of a series of electron-withdrawing and electron-donating substituents ranging from -NO2 to -NH2, an examination of substituent effects has been undertaken with 4-substituted NHC ligands, monosubstituted ethylene derivatives, and 4-substituted styrene derivatives. Natural population, natural bond orbital (NBO), molecular orbital, and bond energy decomposition analysis (EDA) methods have been used to quantify a number of important parameters, including the charge of the coordinated alkenes and the magnitude of alkene→[(NHC)Au](+) and [(NHC)Au](+)→alkene electron donation. EDA methods have also been used to quantify the strength of the [(NHC)Au](+)-(alkene) bond and the impact of both ligand and alkene substitution on different components of the interaction, including polarization, orbital, electrostatic, and Pauli repulsive contributions. Finally, molecular orbital analysis has been used to understand the activation of the alkenes in terms of orbital composition and stabilization within the [(NHC)Au(alkene)](+) complexes relative to the free alkenes. These results provide important insight into the fundamental nature of gold(I)-alkene bonding and the impact of both ligand and alkene substitution on the electronic structure of these complexes.

  6. A mechanistic investigation of anti-elimination in (Z)-1,2-bis(arylseleno)-1-alkenes and their sulfur analogs.

    PubMed

    Tarao, Asami; Tabuchi, Yukako; Sugimoto, Eri; Ikeda, Miki; Uchimoto, Hitomi; Arimitsu, Kenji; Kimura, Hiroyuki; Kawasaki, Ikuo; Kawahata, Masatoshi; Yamaguchi, Kentaro; Nishide, Kiyoharu

    2015-06-07

    The oxidation of (Z)-1,2-bis(arylseleno)-1-alkenes is known to afford alkynyl selenoxides via a unique selenoxide anti-elimination mechanism; however, to date, there have been no mechanistic studies of this reaction. During our studies of this transformation, monoselenoxides 6 and 7 were unexpectedly isolated as stable reaction intermediates. In addition, (77)Se NMR studies of the reaction mixture revealed the presence of an intramolecular Se···O interaction and the formation of alkynyl selenoxides. Meanwhile, even at higher temperatures, the reaction of a (Z)-1,2-bis(arylsulfinyl)-1-alkene, the sulfur analog of (Z)-1,2-bis(arylseleninyl)-1-alkenes, did not proceed via sulfoxide elimination but proceeded via isomerization and disproportionation. Therefore, the intramolecular Se···O interaction can be concluded to play a pivotal role in the anti-elimination reaction.

  7. Biocompatible enzymatic roller pens for direct writing of biocatalytic materials: "do-it-yourself" electrochemical biosensors.

    PubMed

    Bandodkar, Amay J; Jia, Wenzhao; Ramírez, Julian; Wang, Joseph

    2015-06-03

    The development of enzymatic-ink-based roller pens for direct drawing of biocatalytic sensors, in general, and for realizing renewable glucose sensor strips, in particular, is described. The resulting enzymatic-ink pen allows facile fabrication of high-quality inexpensive electrochemical biosensors of any design by the user on a wide variety of surfaces having complex textures with minimal user training. Unlike prefabricated sensors, this approach empowers the end user with the ability of "on-demand" and "on-site" designing and fabricating of biocatalytic sensors to suit their specific requirement. The resulting devices are thus referred to as "do-it-yourself" sensors. The bio-active pens produce highly reproducible biocatalytic traces with minimal edge roughness. The composition of the new enzymatic inks has been optimized for ensuring good biocatalytic activity, electrical conductivity, biocompati-bility, reproducible writing, and surface adherence. The resulting inks are characterized using spectroscopic, viscometric, electrochemical, thermal and microscopic techniques. Applicability to renewable blood glucose testing, epidermal glucose monitoring, and on-leaf phenol detection are demonstrated in connection to glucose oxidase and tyrosinase-based carbon inks. The "do-it-yourself" renewable glucose sensor strips offer a "fresh," reproducible, low-cost biocatalytic sensor surface for each blood test. The ability to directly draw biocatalytic conducting traces even on unconventional surfaces opens up new avenues in various sensing applications in low-resource settings and holds great promise for diverse healthcare, environmental, and defense domains. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Combinatorial metabolic engineering of Saccharomyces cerevisiae for terminal alkene production.

    PubMed

    Chen, Binbin; Lee, Dong-Yup; Chang, Matthew Wook

    2015-09-01

    Biological production of terminal alkenes has garnered a significant interest due to their industrial applications such as lubricants, detergents and fuels. Here, we engineered the yeast Saccharomyces cerevisiae to produce terminal alkenes via a one-step fatty acid decarboxylation pathway and improved the alkene production using combinatorial engineering strategies. In brief, we first characterized eight fatty acid decarboxylases to enable and enhance alkene production. We then increased the production titer 7-fold by improving the availability of the precursor fatty acids. We additionally increased the titer about 5-fold through genetic cofactor engineering and gene expression tuning in rich medium. Lastly, we further improved the titer 1.8-fold to 3.7 mg/L by optimizing the culturing conditions in bioreactors. This study represents the first report of terminal alkene biosynthesis in S. cerevisiae, and the abovementioned combinatorial engineering approaches collectively increased the titer 67.4-fold. We envision that these approaches could provide insights into devising engineering strategies to improve the production of fatty acid-derived biochemicals in S. cerevisiae.

  9. Intramolecular Alkene Aminocarbonylation Using Concerted Cycloadditions of Amino-Isocyanates.

    PubMed

    Ivanovich, Ryan A; Clavette, Christian; Vincent-Rocan, Jean-François; Roveda, Jean-Grégoire; Gorelsky, Serge I; Beauchemin, André M

    2016-06-01

    The ubiquity of nitrogen heterocycles in biologically active molecules challenges synthetic chemists to develop a variety of tools for their construction. While developing metal-free hydroamination reactions of hydrazine derivatives, it was discovered that carbazates and semicarbazides can also lead to alkene aminocarbonylation products if nitrogen-substituted isocyanates (N-isocyanates) are formed in situ as reactive intermediates. At first this reaction required high temperatures (150-200 °C), and issues included competing hydroamination and N-isocyanate dimerization pathways. Herein, improved conditions for concerted intramolecular alkene aminocarbonylation with N-isocyanates are reported. The use of βN-benzyl carbazate precursors allows the effective minimization of N-isocyanate dimerization. Diminished dimerization leads to higher yields of alkene aminocarbonylation products, to reactivity at lower temperatures, and to an improved scope for a reaction sequence involving alkene aminocarbonylation followed by 1,2-migration of the benzyl group. Furthermore, fine-tuning of the blocking (masking) group on the N-isocyanate precursor, and reaction conditions relying on base catalysis for N-isocyanate formation from simpler precursors resulted in room temperature reactivity, consequently minimizing the competing hydroamination pathway. Collectively, this work highlights that controlled reactivity of aminoisocyanates is possible, and provides a broadly applicable alkene aminocarbonylation approach to heterocycles possessing the β-aminocarbonyl motif.

  10. Synthesis of Polycyclic Nitrogen Heterocycles via Cascade Pd-Catalyzed Alkene Carboamination/Diels-Alder Reactions.

    PubMed

    White, Derick R; Wolfe, John P

    2015-05-15

    Cascade Pd-catalyzed alkene carboamination/Diels-Alder reactions between bromodienes and amines bearing two pendant alkenes are described. These transformations generate 4 bonds, 3 rings, and 3-5 stereocenters to afford polycyclic nitrogen heterocycles with high diastereoselectivity.

  11. Conversion of allylic alcohols to stereodefined trisubstituted alkenes: a complementary process to the Claisen rearrangement.

    PubMed

    Belardi, Justin K; Micalizio, Glenn C

    2008-12-17

    A stereoselective method for the conversion of allylic alcohols to (Z)-trisubstituted alkenes is presented. Overall, the reaction sequence described is stereochemically complementary to related Claisen rearrangement reactions--processes that typically deliver the stereoisomeric trisubstituted alkene containing products.

  12. Cloning, Expression, Characterization, and Biocatalytic Investigation of the 4-Hydroxyacetophenone Monooxygenase from Pseudomonas putida JD1▿ †

    PubMed Central

    Rehdorf, Jessica; Zimmer, Christian L.; Bornscheuer, Uwe T.

    2009-01-01

    While the number of available recombinant Baeyer-Villiger monooxygenases (BVMOs) has grown significantly over the last few years, there is still the demand for other BVMOs to expand the biocatalytic diversity. Most BVMOs that have been described are dedicated to convert efficiently cyclohexanone and related cyclic aliphatic ketones. To cover a broader range of substrate types and enantio- and/or regioselectivities, new BVMOs have to be discovered. The gene encoding a BVMO identified in Pseudomonas putida JD1 converting aromatic ketones (HAPMO; 4-hydroxyacetophenone monooxygenase) was amplified from genomic DNA using SiteFinding-PCR, cloned, and functionally expressed in Escherichia coli. Furthermore, four other open reading frames could be identified clustered around this HAPMO. It has been suggested that these proteins, including the HAPMO, might be involved in the degradation of 4-hydroxyacetophenone. Substrate specificity studies revealed that a large variety of other arylaliphatic ketones are also converted via Baeyer-Villiger oxidation into the corresponding esters, with preferences for para-substitutions at the aromatic ring. In addition, oxidation of aldehydes and some heteroaromatic compounds was observed. Cycloketones and open-chain ketones were not or poorly accepted, respectively. It was also found that this enzyme oxidizes aromatic ketones such as 3-phenyl-2-butanone with excellent enantioselectivity (E ≫100). PMID:19251889

  13. Synthesis and characterization of supported heteropolymolybdate nanoparticles between silicate layers of Bentonite with enhanced catalytic activity for epoxidation of alkenes

    SciTech Connect

    Salavati, Hossein; Rasouli, Nahid

    2011-11-15

    Highlights: {yields} The PVMo and nanocomposite catalyst (PVMo/Bentonite) as catalyst for epoxidation of alkenes. {yields} The composite catalyst showed higher catalytic activity than parent heteropolymolybdate (PVMo). {yields}The use of ultrasonic irradiation increased the conversions and reduced the reaction times. {yields} The H{sub 2}O{sub 2} is a green and eco-friendly oxidant in this catalytic system. -- Abstract: A new heterogeneous catalyst (PVMo/Bentonite) consisting of vanadium substituted heteropolymolybdate with Keggin-type structure Na{sub 5}[PV{sub 2}Mo{sub 10}O{sub 40}].14H{sub 2}O (PVMo) supported between silicate layers of bentonite has been synthesized by impregnation method and characterized using X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, UV-vis diffuse reflectance spectroscopy, transmission electron microscopy and elemental analysis. X-ray diffraction and scanning electron microscopy analysis indicated that PVMo was finely dispersed into layers of bentonite as support. The PVMo/Bentonite used as an efficient heterogeneous catalyst for epoxidation of alkenes. Various cyclic and linear alkenes were oxidized into the corresponding epoxides in high yields and selectivity with 30% aqueous H{sub 2}O{sub 2}. The catalyst was reused several times, without observable loss of activity and selectivity. The obtained results showed that the catalytic activity of the PVMo/Bentonite was higher than that of pure heteropolyanion (PVMo).

  14. Intramolecular Aminocyanation of Alkenes via N–CN Bond Cleavage**

    PubMed Central

    Pan, Zhongda; Pound, Sarah M.; Rondla, Naveen R.; Douglas, Christopher J.

    2014-01-01

    A metal-free, Lewis acid-promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, leading an formal cleavage of the N-CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with 13C suggest a fully intramolecular cyclization pattern due to lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air. PMID:24719371

  15. Intramolecular aminocyanation of alkenes by N-CN bond cleavage.

    PubMed

    Pan, Zhongda; Pound, Sarah M; Rondla, Naveen R; Douglas, Christopher J

    2014-05-12

    A metal-free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, thus leading to a formal cleavage of the N-CN bonds in conjunction with vicinal addition of sulfonamide and nitrile groups across an alkene. This method enables atom-economical access to indolines and tetrahydroquinolines in excellent yields, and provides a complementary strategy for regioselective alkene difunctionalizations with sulfonamide and nitrile groups. Labeling experiments with (13)C suggest a fully intramolecular cyclization pattern due to the lack of label scrambling in double crossover experiments. Catalysis with Lewis acid is realized and the reaction can be conducted under air. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.

    PubMed

    Bovino, Michael T; Liwosz, Timothy W; Kendel, Nicole E; Miller, Yan; Tyminska, Nina; Zurek, Eva; Chemler, Sherry R

    2014-06-16

    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. The mechanism for iron-catalyzed alkene isomerization in solution

    SciTech Connect

    Sawyer, Karma R.; Glascoe, Elizabeth A.; Cahoon, James F.; Schlegel, Jacob P.; Harris, Charles B.

    2008-05-27

    Here we report nano- through microsecond time-resolved IR experiments of iron-catalyzed alkene isomerization in room-temperature solution. We have monitored the photochemistry of a model system, Fe(CO){sub 4}({eta}{sup 2}-1-hexene), in neat 1-hexene solution. UV-photolysis of the starting material leads to the dissociation of a single CO to form Fe(CO){sub 3}({eta}{sup 2}-1-hexene), in a singlet spin state. This CO loss complex shows a dramatic selectivity to form an allyl hydride, HFe(CO){sub 3}({eta}{sup 3}-C{sub 6}H{sub 11}), via an internal C-H bond-cleavage reaction in 5-25 ns. We find no evidence for the coordination of an alkene molecule from the bath to the CO loss complex, but do observe coordination to the allyl hydride, indicating that it is the key intermediate in the isomerization mechanism. Coordination of the alkene ligand to the allyl hydride leads to the formation of the bis-alkene isomers, Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) and Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2}. Because of the thermodynamic stability of Fe(CO){sub 3}({eta}{sup 2}-1-hexene)({eta}{sup 2}-2-hexene) over Fe(CO){sub 3}({eta}{sup 2}-1-hexene){sub 2} (ca. 12 kcal/mol), nearly 100% of the alkene population will be 2-alkene. The results presented herein provide the first direct evidence for this mechanism in solution and suggest modifications to the currently accepted mechanism.

  18. Joint toxic effects of the type-2 alkene electrophiles.

    PubMed

    Zhang, Lihai; Geohagen, Brian C; Gavin, Terrence; LoPachin, Richard M

    2016-07-25

    Human populations are exposed to complex environmental mixtures of acrolein, methylvinyl ketone (MVK) and other type-2 alkenes. Many members of this chemical class are electrophiles that possess a common molecular mechanism of toxicity; i.e., protein inactivation via formation of stable cysteine adducts. Therefore, acute or chronic exposure to type-2 alkene mixtures could represent a health risk due to additive or synergistic interactions among component chemicals. Despite this risk, there is little experimental information regarding the joint effects of type-2 alkenes. In the present study we used sum of toxic units (TUsum = ∑TUi) to assess the relative toxicity of different type-2 alkene mixtures. These studies involved well characterized environmental type-2 alkene toxicants and included amide (acrylamide; ACR), ketone (methyl vinyl ketone; MVK), aldehyde (2-ethylacrolein; EA) and ester (methyl acrylate; MA) derivatives. In chemico analyses revealed that both binary and ternary mixtures could deplete thiol groups according to an additive joint effect at equitoxic and non-equitoxic ratios; i.e., TUsum = 1.0 ± 0.20. In contrast, analyses of joint effects in SNB19 cell cultures indicated that different permutations of type-2 alkene mixtures produced mostly synergistic joint effects with respect to cell lethality; i.e., TUsum < 0.80. A mixture of ACR and MA was shown to produce joint toxicity in a rat model. This mixture accelerated the onset and development of neurotoxicity relative to the effects of the individual toxicants. Synergistic effects in biological models might occur when different cellular proteomes are targeted, whereas additive effects develop when the mixtures encompasses a similar proteome. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  19. Joint Toxic Effects of the Type-2 Alkene Electrophiles

    PubMed Central

    Zhang, Lihai; Geohagen, Brian C.; Gavin, Terrence; LoPachin, Richard M.

    2016-01-01

    Human populations are exposed to complex environmental mixtures of acrolein, methylvinyl ketone (MVK) and other type-2 alkenes. Many members of this chemical class are electrophiles that possess a common molecular mechanism of toxicity; i.e., protein inactivation via formation of stable cysteine adducts. Therefore, acute or chronic exposure to type-2 alkene mixtures could represent a health risk due to additive or synergistic interactions among component chemicals. Despite this risk, there is little experimental information regarding the joint effects of type-2 alkenes. In the present study we used sum of toxic units (TUsum = ΣTUi) to assess the relative toxicity of different type-2 alkene mixtures. These studies involved well characterized environmental type-2 alkene toxicants and included amide (acrylamide; ACR), ketone (methyl vinyl ketone; MVK), aldehyde (2-ethylacrolein; EA) and ester (methyl acrylate; MA) derivatives. In chemico analyses revealed that both binary and ternary mixtures could deplete thiol groups according to an additive joint effect at equitoxic and non-equitoxic ratios; i.e., TUsum = 1.0 ± 0.20. In contrast, analyses of joint effects in SNB19 cell cultures indicated that different permutations of type-2 alkene mixtures produced mostly synergistic joint effects with respect to cell lethality; i.e., TUsum < 0.80. A mixture of ACR and MA was shown to produce joint toxicity in a rat model. This mixture accelerated the onset and development of neurotoxicity relative to the effects of the individual toxicants. Synergistic effects in biological models might occur when different cellular proteomes are targeted, whereas additive effects develop when the mixtures encompasses a similar proteome. PMID:27288850

  20. 40 CFR 721.3780 - Substituted and disubstituted tetrafluoro alkenes (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... tetrafluoro alkenes (generic). 721.3780 Section 721.3780 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3780 Substituted and disubstituted tetrafluoro alkenes... substance identified generically as substituted and disubstituted tetrafluoro alkene (PMN P-84-105) is...

  1. 40 CFR 721.3780 - Substituted and disubstituted tetrafluoro alkenes (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... tetrafluoro alkenes (generic). 721.3780 Section 721.3780 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3780 Substituted and disubstituted tetrafluoro alkenes... substance identified generically as substituted and disubstituted tetrafluoro alkene (PMN P-84-105) is...

  2. 40 CFR 721.3780 - Substituted and disubstituted tetrafluoro alkenes (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... tetrafluoro alkenes (generic). 721.3780 Section 721.3780 Protection of Environment ENVIRONMENTAL PROTECTION... New Uses for Specific Chemical Substances § 721.3780 Substituted and disubstituted tetrafluoro alkenes... substance identified generically as substituted and disubstituted tetrafluoro alkene (PMN P-84-105) is...

  3. Facile synthesis of Z-alkenes via uphill catalysis.

    PubMed

    Singh, Kamaljeet; Staig, Shannon J; Weaver, Jimmie D

    2014-04-09

    Catalytic access to thermodynamically less stable Z-alkenes has recently received considerable attention. These approaches have relied upon kinetic control of the reaction to arrive at the thermodynamically less stable geometrical isomer. Herein, we present an orthogonal approach which proceeds via photochemically catalyzed isomerization of the thermodynamic E-alkene to the less stable Z-isomer which occurs via a photochemical pumping mechanism. We consider two potential mechanisms. Importantly, the reaction conditions are mild, tolerant, and operationally simple and will be easily implemented.

  4. Difluorocarbene Addition to Alkenes and Alkynes in Continuous Flow.

    PubMed

    Rullière, Pauline; Cyr, Patrick; Charette, André B

    2016-05-06

    The first in-flow difluorocarbene generation and addition to alkenes and alkynes is reported. The application of continuous flow technology allowed for the controlled generation of difluorocarbene from TMSCF3 and a catalytic quantity of NaI. The in situ generated electrophilic carbene reacts smoothly with a broad range of alkenes and alkynes, allowing the synthesis of the corresponding difluorocyclopropanes and difluorocyclopropenes. The reaction is complete within a 10 min residence time at high reaction concentrations. With a production flow rate of 1 mmol/min, continuous flow chemistry enables scale up of this process in a green, atom-economic, and safe manner.

  5. Zirconium-Catalyzed Asymmetric Carboalumination of Unactivated Terminal Alkenes.

    PubMed

    Xu, Shiqing; Negishi, Ei-Ichi

    2016-10-18

    Carbometalation of alkenes with stereocontrol offers an important opportunity for asymmetric C-C bond formation. However, the scope of catalytic stereoselective carbometalation of alkenes had until recently been limited to electronically biased alkenes or those with the presence of directing groups or other auxiliary functionalities to overcome the challenge associated with regio- and stereoselectivity. Catalytic asymmetric carbometalation of unactivated alkenes on the other hand remained as a formidable challenge. To address this long-standing problem, we sought to develop Zr-catalyzed asymmetric carboalumination of alkenes (namely, ZACA reaction) encouraged by our discovery of Zr-catalyzed alkyne carboalumination in 1978. Zr-catalyzed methylalumination of alkynes (ZMA) shows high regioselectivity and nearly perfect stereoselectivity. Its mechanistic studies have revealed that the ZMA reaction involves acyclic carbometalation with "superacidic" bimetallic reagents generated by interaction between two Lewis acids, i.e., alkylalanes and 16-electron zirconocene derivatives through dynamic polarization and ate complexation, affectionately termed as the "two-is-better-than-one" principle. With the encouraging results of Zr-catalyzed carboalumination of alkynes in hand, we sought to develop its alkene version for discovering a catalytic asymmetric C-C bond-forming reaction by using alkylalanes and suitable chiral zirconocene derivatives, which would generate "superacidic" bimetallic species to promote the desired carbometalation of alkenes. However, this proved to be quite challenging. Three major competing side reactions occur, i.e., (i) β-H transfer hydrometalation, (ii) bimetallic cyclic carbometalation, and (iii) Ziegler-Natta polymerization. The ZACA reaction was finally discovered by employing Erker's (-)-(NMI)2ZrCl2 as the catalyst and chlorinated hydrocarbon as solvent to suppress the undesired side reactions mentioned above. The ZACA reaction has evolved as a

  6. Alkenes with antioxidative activities from Murraya koenigii (L.) Spreng.

    PubMed

    Ma, Qin-Ge; Xu, Kun; Sang, Zhi-Pei; Wei, Rong-Rui; Liu, Wen-Min; Su, Ya-Lun; Yang, Jian-Bo; Wang, Ai-Guo; Ji, Teng-Fei; Li, Lu-Jun

    2016-02-01

    Four new alkenes (1-4), and six known alkenes (5-12) were isolated from Murraya koenigii (L.) Spreng. Their structures were elucidated on the basis of spectroscopic analyses and references. Compounds (1-12) were evaluated for antioxidative activities. Among them, compounds 1, 2, 4, and 7 exhibited significant antioxidative activities using 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay with IC50=21.4-49.5 μM. The known compounds (5-12) were isolated from this plant for the first time. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Unidirectional light-driven molecular motors based on overcrowded alkenes.

    PubMed

    Cnossen, Arjen; Browne, Wesley R; Feringa, Ben L

    2014-01-01

    Over the last two decades, interest in nanotechnology has led to the design and synthesis of a toolbox of nanoscale versions of macroscopic devices and components. In molecular nanotechnology, linear motors based on rotaxanes and rotary motors based on overcrowded alkenes are particularly promising for performing work at the nanoscale. In this chapter, progress on light-driven molecular motors based on overcrowded alkenes is reviewed. Both the so-called first and second generation molecular motors are discussed, as well as their potential applications.

  8. New osmium-based reagent for the dihydroxylation of alkenes.

    PubMed

    Donohoe, Timothy J; Harris, Robert M; Butterworth, Sam; Burrows, Jeremy N; Cowley, Andrew; Parker, Jeremy S

    2006-06-09

    The cis dihydroxylation of alkenes is most efficiently accomplished by reaction with osmium tetroxide. Recently, the expense and toxicity of osmium tetroxide have led to a number of attempts to harness alternative osmium-based reagents, including microencapsulation and solid support techniques. We describe here the development of a new nonvolatile, stable, and recoverable osmium-based reagent devised for the stoichiometric cis dihydroxylation of alkenes. Although attempts to make this new dihydroxylation work with catalytic amounts of this reagent were unsuccessful, we did develop a sensitive test for free osmium tetroxide leached from the reagent in situ: this test may well have uses in probing future applications of derivatized osmium reagents.

  9. The syn/anti-Dichotomy in the Palladium-Catalyzed Addition of Nucleophiles to Alkenes

    PubMed Central

    Kočovský, Pavel; Bäckvall, Jan-E

    2015-01-01

    In this review the stereochemistry of palladium-catalyzed addition of nucleophiles to alkenes is discussed, and examples of these reactions in organic synthesis are given. Most of the reactions discussed involve oxygen and nitrogen nucleophiles; the Wacker oxidation of ethylene has been reviewed in detail. An anti-hydroxypalladation in the Wacker oxidation has strong support from both experimental and computational studies. From the reviewed material it is clear that anti-addition of oxygen and nitrogen nucleophiles is strongly favored in intermolecular addition to olefin–palladium complexes even if the nucleophile is coordinated to the metal. On the other hand, syn-addition is common in the case of intramolecular oxy- and amidopalladation as a result of the initial coordination of the internal nucleophile to the metal. PMID:25378278

  10. Effect of increasing dietary antioxidants on concentrations of vitamin E and total alkenals in serum of dogs and cats.

    PubMed

    Jewell, D E; Toll, P W; Wedekind, K J; Zicker, S C

    2000-01-01

    Oxidative damage to DNA, proteins, and lipids has been implicated as a contributor to aging and various chronic diseases. The presence of total alkenals (malondialdehyde and 4-hydroxyalkenals) in blood or tissues is an indicator of lipid peroxidation, which may be a result of in vivo oxidative reactions. Vitamin E functions as a chain-breaking antioxidant that prevents propagation of free radical damage in biologic membranes. This 6-week dose-titration study was conducted to assess the effect of selected dietary vitamin E levels on byproducts of in vivo oxidative reactions in dogs and cats. Forty healthy adult dogs and 40 healthy adult cats were assigned to four equal groups per species in a complete random block design. A control group for both dogs and cats was fed dry food containing 153 and 98 IU vitamin E/kg of food (as fed), respectively. Canine and feline treatment groups were fed the same basal dry food with vitamin E added at three different concentrations. The total analyzed dietary vitamin E levels for the canine treatment groups were 293, 445, and 598 IU vitamin E/kg of food, as fed. The total analyzed dietary vitamin E levels for the feline treatment groups were 248, 384, and 540 IU vitamin E/kg of food, as fed. Increasing levels of dietary vitamin E in dog and cat foods caused significant increases in serum vitamin E levels compared with baseline values. Although all treatments increased concentrations of vitamin E in serum, all were not effective at decreasing serum alkenal levels. The thresholds for significant reduction of serum alkenal concentrations in dogs and cats were 445 and 540 IU vitamin E/kg of food, respectively, on an as-fed basis. The results of this study show that normal dogs and cats experience oxidative damage and that increased dietary levels of antioxidants may decrease in vivo measures of oxidative damage.

  11. Increased functionality of methyl oleate using alkene metathesis

    USDA-ARS?s Scientific Manuscript database

    A series of alkene cross metathesis reactions were performed using a homogeneous ruthenium based catalyst. Using this technology, a variety of functional groups can be incorporated into the biobased starting material, methyl oleate. Trans-stilbene, styrene, methyl cinnamate and hexen-3-ol were all s...

  12. Synthesis of Cyclic Guanidines via Pd-Catalyzed Alkene Carboamination

    PubMed Central

    Zavesky, Blane P.; Babij, Nicholas R.; Fritz, Jonathan A.

    2013-01-01

    A new approach to the synthesis of substituted 5-membered cyclic guanidines is described. Palladium-catalyzed alkene carboamination reactions between acyclic N-allyl guanidines and aryl or alkenyl halides provide these products in good yield. This method allows access to a number of different cyclic guanidine derivatives in only two steps from readily available allylic amines. PMID:24147839

  13. Heuristical Strategies on the Study Theme "The Unsaturated Hydrocarbons -- Alkenes"

    ERIC Educational Resources Information Center

    Naumescu, Adrienne Kozan; Pasca, Roxana-Diana

    2011-01-01

    The influence of heuristical strategies upon the level of two experimental classes is studied in this paper. The didactic experiment took place at secondary school in Cluj-Napoca, in 2008-2009 school year. The study theme "The Unsaturated Hydrocarbons--Alkenes" has been efficiently learned by using the most active methods: laboratory…

  14. Phosphinoyl Radical-Initiated α,β-Aminophosphinoylation of Alkenes.

    PubMed

    Li, Jian-An; Zhang, Pei-Zhi; Liu, Kui; Shoberu, Adedamola; Zou, Jian-Ping; Zhang, Wei

    2017-09-01

    A new double functionalization reaction of alkenes through AgNO3-mediated phosphinoyl radical addition followed by Cu(II)-catalyzed amination is introduced. This one-pot, three-component reaction is performed under mild conditions to afford α,β-aminophosphinoylation products.

  15. Laboratory spectroscopic analyses of electron irradiated alkanes and alkenes in solar system ices

    NASA Astrophysics Data System (ADS)

    Hand, K. P.; Carlson, R. W.

    2012-03-01

    We report results from laboratory experiments of 10 keV electron irradiation of thin ice films of water and short-chain hydrocarbons at ˜10-8 Torr and temperatures ranging from 70-100 K. Hydrocarbon mixtures include water with C3H8, C3H6, C4H10 (butane and isobutane), and C4H8, (1-butene and cis/trans-2-butene). The double bonds of the alkenes in our initial mixtures were rapidly destroyed or converted to single carbon bonds, covalent bonds with hydrogen, bonds with -OH (hydroxyl), bonds with oxygen (C-O), or double bonds with oxygen (carbonyl). Spectra resulting from irradiation of alkane and alkene ices are largely indistinguishable; the initial differences in film composition are destroyed and the resulting mixture includes long-chain, branched aliphatics, aldehydes, ketones, esters, and alcohols. Methane was observed as a product during radiolysis but CO was largely absent. We find that while some of the carbon is oxidized and lost to CO2 formation, some carbon is sequestered into highly refractory, long-chain aliphatic compounds that remain as a thin residue even after the ice film has been raised to standard temperature and pressure. We conclude that the high availability of hydrogen in our experiments leads to the formation of the formyl radical which then serves as the precursor for formaldehyde and polymerization of longer hydrocarbon chains.

  16. Mechanistic insight into the photoredox catalysis of anti-Markovnikov alkene hydrofunctionalization reactions

    SciTech Connect

    Romero, Nathan A.; Nicewicz, David A.

    2014-11-12

    Here, we describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step using DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr+ is observed to engage in off-cycle adduct formation, presumably as buildup of PhS becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence.

  17. Mechanistic insight into the photoredox catalysis of anti-Markovnikov alkene hydrofunctionalization reactions

    DOE PAGES

    Romero, Nathan A.; Nicewicz, David A.

    2014-11-12

    Here, we describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step usingmore » DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr+ is observed to engage in off-cycle adduct formation, presumably as buildup of PhS– becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence.« less

  18. Electron transfer reactions in the alkene mono-oxygenase complex from Nocardia corallina B-276.

    PubMed Central

    Gallagher, S C; Cammack, R; Dalton, H

    1999-01-01

    Nocardia corallina B-276 possesses a multi-component enzyme, alkene mono-oxygenase (AMO), that catalyses the stereoselective epoxygenation of alkenes. The reductase component of this system has been shown by EPR and fluorescence spectroscopy to contain two prosthetic groups, an FAD centre and a [2Fe-2S] cluster. The role of these centres in the epoxygenation reaction was determined by midpoint potential measurements and electron transfer kinetics. The order of potentials of the prosthetic groups of the reductase were FAD/FAD.=-216 mV, [2Fe-2S]/[2Fe-2S].=-160 mV and FAD./FAD.=-134 mV. Combined, these data implied that the reductase component supplied the energy required for the epoxygenation reaction and allowed a prediction of the mechanism of electron transfer within the AMO complex. The FAD moiety was reduced by bound NADH in a two-electron reaction. The electrons were then transported to the [2Fe-2S] centre one at a time, which in turn reduced the di-iron centre of the epoxygenase. Reduction of the di-iron centre is required for oxygen binding and substrate oxidation. PMID:10085230

  19. Mechanistic Insight into the Photoredox Catalysis of Anti-Markovnikov Alkene Hydrofunctionalization Reactions

    PubMed Central

    2015-01-01

    We describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr+) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step using DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr+ is observed to engage in off-cycle adduct formation, presumably as buildup of PhS− becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence. PMID:25390821

  20. Mechanistic insight into the photoredox catalysis of anti-markovnikov alkene hydrofunctionalization reactions.

    PubMed

    Romero, Nathan A; Nicewicz, David A

    2014-12-10

    We describe our efforts to understand the key mechanistic aspects of the previously reported alkene hydrofunctionalization reactions using 9-mesityl-10-methylacridinium (Mes-Acr(+)) as a photoredox catalyst. Importantly, we are able to detect alkene cation radical intermediates, and confirm that phenylthiyl radical is capable of oxidizing the persistent acridinyl radical in a fast process that unites the catalytic activity of the photoredox and hydrogen atom transfer (HAT) manifolds. Additionally, we present evidence that diphenyl disulfide ((PhS)2) operates on a common catalytic cycle with thiophenol (PhSH) by way of photolytic cleaveage of the disulfide bond. Transition structure analysis of the HAT step using DFT reveals that the activation barrier for H atom donation from PhSH is significantly lower than 2-phenylmalononitrile (PMN) due to structural reorganization. In the early stages of the reaction, Mes-Acr(+) is observed to engage in off-cycle adduct formation, presumably as buildup of PhS(-) becomes significant. The kinetic differences between PhSH and (PhS)2 as HAT catalysts indicate that the proton transfer step may have significant rate limiting influence.

  1. Evaluation of two MCM v3.1 alkene mechanisms using indoor environmental chamber data

    NASA Astrophysics Data System (ADS)

    Hynes, R. G.; Angove, D. E.; Saunders, S. M.; Haverd, V.; Azzi, M.

    Photo-oxidation experiments on propene-NO x-air and 1-butene-NO x-air mixtures were performed in the CSIRO indoor environmental chamber. These data were used to test the alkene sub-mechanisms from the Master Chemical Mechanism version 3.1 (MCM v3.1). A comparison of measured and modelled propene-NO x data showed that the mechanisms required the inclusion of O( 3P)+parent alkene reactions in order to adequately model the results over a wide range of VOC/NO x ratios. Sensitivity studies were performed on propene-NO x and 1-butene-NO x simulations to determine the effect of uncertainties in the chamber parameters and key photolysis rates on the O 3, and NO x profiles. The low VOC/NO x propene simulations were sensitive to the formaldehyde (HCHO) photolysis channel that produces HO 2 radicals and to the presence of O( 3P) reactions. For the higher VOC/NO x propene simulations, the O 3, and NO x results were more sensitive to small changes in the initial HONO and NO 2 concentrations.

  2. Cobalt-Catalyzed [2π + 2π] Cycloadditions of Alkenes: Scope, Mechanism, and Elucidation of Electronic Structure of Catalytic Intermediates.

    PubMed

    Schmidt, Valerie A; Hoyt, Jordan M; Margulieux, Grant W; Chirik, Paul J

    2015-06-24

    Aryl-substituted bis(imino)pyridine cobalt dinitrogen compounds, ((R)PDI)CoN2, are effective precatalysts for the intramolecular [2π + 2π] cycloaddition of α,ω-dienes to yield the corresponding bicyclo[3.2.0]heptane derivatives. The reactions proceed under mild thermal conditions with unactivated alkenes, tolerating both amine and ether functional groups. The overall second order rate law for the reaction, first order with respect to both the cobalt precatalyst and the substrate, in combination with electron paramagnetic resonance (EPR) spectroscopic studies established the catalyst resting state as dependent on the identity of the precatalyst and diene substrate. Planar S = ½ κ(3)-bis(imino)pyridine cobalt alkene and tetrahedral κ(2)-bis(imino)pyridine cobalt diene complexes were observed by EPR spectroscopy and in the latter case structurally characterized. The hemilabile chelate facilitates conversion of a principally ligand-based singly occupied molecular orbital (SOMO) in the cobalt dinitrogen and alkene compounds to a metal-based SOMO in the diene intermediates, promoting C-C bond-forming oxidative cyclization. Structure-activity relationships on bis(imino)pyridine substitution were also established with 2,4,6-tricyclopentyl-substituted aryl groups, resulting in optimized catalytic [2π + 2π] cycloaddition. The cyclopentyl groups provide a sufficiently open metal coordination sphere that encourages substrate coordination while remaining large enough to promote a challenging, turnover-limiting C(sp(3))-C(sp(3)) reductive elimination.

  3. Theoretical determination of molecular structure and conformation. 18. On the formation of epoxides during the ozonolysis of alkenes

    SciTech Connect

    Cremer, D.; Bock, C.W.

    1986-06-11

    The reaction of carbonyl oxide (CH/sub 2/OO) and ethylene has been investigated by ab initio techniques. According to theoretical results, carbonyl oxide can act as an oxygen-transfer agent, thus leading to epoxide and aldehyde: C/sub 2/H/sub 4/ + CH/sub 2/OO ..-->.. CH/sub 2/OCH/sub 2/ + CH/sub 2/O. The calculated transition-state energies of the various epoxidation modes are 4-8 kcal/mol, which are comparable to activation energies of cycloaddition (cycloreversion) reactions encountered in the ozonolysis of alkenes. Epoxidation of alkene by carbonyl oxide is best described as a S/sub N/2 reaction on the terminal oxygen atom of carbonyl oxide. The preferred collision mode of the O-transfer reaction can be rationalized on the basis of frontier orbital interactions. Apart from epoxidation, carbonyl oxide can add to ethylene, yielding 1,2-dioxolane. The energy requirements of the cycloaddition are equivalent to those of the epoxidation. However, 1,2-dioxolanes will only be observed under normal ozonolysis conditions if the excess energy generated in the cycloaddition reaction is readily dissipated. Otherwise, 1,2-dioxolanes will immediately decompose, again yielding, among other products, epoxides.

  4. Structure-Odor Relationships of (Z)-3-Alken-1-ols, (Z)-3-Alkenals, and (Z)-3-Alkenoic Acids.

    PubMed

    Lorber, Katja; Zeh, Gina; Regler, Johanna; Buettner, Andrea

    2017-01-09

    (Z)-3-Unsaturated volatile acids, alcohols, and aldehydes are commonly found in foods and other natural sources, playing a vital role in the attractiveness of foods but also as compounds with chemocommunicative function in entomology. However, a systematic investigation of their smell properties, especially regarding humans, has not been carried out until today. To close this gap, the odor thresholds in air and odor qualities of homologous series of (Z)-3-alken-1-ols, (Z)-3-alkenals, and (Z)-3-alkenoic acids were determined by gas chromatography-olfactometry. It was found that the odor qualities in the series of the (Z)-3-alken-1-ols and (Z)-3-alkenals changed, with increasing chain length, from grassy, green to an overall fatty and citrus-like, soapy character. On the other hand, the odor qualities of the (Z)-3-alkenoic acids changed successively from cheesy, sweaty via plastic-like, to waxy in their homologous series. With regard to their odor potencies, the lowest thresholds in air were found for (Z)-3-hexenal, (Z)-3-octenoic acid, and (Z)-3-octenal.

  5. Novel Oxidation of Cyclosporin A: Preparation of Cyclosporin Methyl Vinyl Ketone (Cs-MVK)

    USDA-ARS?s Scientific Manuscript database

    Cyclosporin A (CsA) was converted into cyclosporin methyl vinyl ketone (Cs-MVK) by either a biocatalytic method utilizing 1-hydroxybenzotriazole-mediated laccase oxidation or by a chemical oxidation using t-butyl hydroperoxide and potassium ­periodate as co-oxidants. Cs-MVK is a novel, versatile sy...

  6. Spectroscopic and biocatalytic properties of a chlorophyll-containing extract in silica gel

    NASA Astrophysics Data System (ADS)

    Lipke, Agnieszka; Trytek, Mariusz; Fiedurek, Jan; Majdan, Marek; Janik, Ewa

    2013-11-01

    UV-Vis absorption and fluorescence spectra of chlorophyll a (in the form of spinach extract) in acetone solution and in silica gel showed a predominance of pigment dimers in its overall concentration and an evident transformation of chlorophyll a to pheophytin with time. The dimerization constant of chlorophyll a in acetone was log Kdim = 2.14, whereas the constants for chlorophyll a and pheophytin a in alcogel were log Kdim = 4.70 and log Kdim = 5.22, respectively. Biocatalytic experiments indicated the possibility of using the pigment embedded in silica gel, i.e. mainly its dimeric form, for biotransformation of α-pinene to pinocarveyl hydroperoxide, trans-pinocarveol, pinocarvone and myrtenal. The advantage of a heterogeneous biocatalytic system (composed of a solvent and silica gel) over a homogeneous system (single phase of chloroform) is the possibility of reusing the biocatalyst with about 10% preservation of its activity.

  7. Ligand development in the Ni-catalyzed hydrocyanation of alkenes.

    PubMed

    Bini, Laura; Müller, Christian; Vogt, Dieter

    2010-11-28

    The addition of HCN to alkenes is a very useful reaction for the synthesis of functional organic substrates. Industrially the nickel-catalyzed hydrocyanation has gained considerable importance mainly because of the production of adiponitrile in the DuPont process. In this process the hydrocyanation of butadiene is carried out using aryl phosphite-modified nickel catalyst. Since the performance of organo-transition metal complexes is largely determined by the ligand environment of the metal, fundamental understanding and ligand development is of pivotal importance for any progress. This feature article gives an account of the development and application of different mono- and bidentate phosphorus-based ligands in the Ni-catalyzed hydrocyanation reaction of alkenes. Special attention will be paid to the development of insight and understanding of the ligand structural and electronic properties towards the improvement of the catalyst performance in terms of stability, activity, and selectivity.

  8. Biocatalytic Synthesis of Chiral Alcohols and Amino Acids for Development of Pharmaceuticals

    PubMed Central

    Patel, Ramesh N.

    2013-01-01

    Chirality is a key factor in the safety and efficacy of many drug products and thus the production of single enantiomers of drug intermediates and drugs has become increasingly important in the pharmaceutical industry. There has been an increasing awareness of the enormous potential of microorganisms and enzymes derived there from for the transformation of synthetic chemicals with high chemo-, regio- and enatioselectivities. In this article, biocatalytic processes are described for the synthesis of chiral alcohols and unntural aminoacids for pharmaceuticals. PMID:24970190

  9. Enantiogroup-differentiating biocatalytic reductions of prochiral Cs -symmetrical dicarbonyl compounds to meso compounds.

    PubMed

    Skoupi, Marc; Vaxelaire, Carine; Strohmann, Carsten; Christmann, Mathias; Niemeyer, Christof M

    2015-06-08

    The stereoselective reduction of symmetrical prochiral dicarbonyl compounds bearing enantiotopic carbonyl groups yields several stereogenic centers in one step. In a proof-of-concept study, a new approach is described for the enzymatic desymmetrization of 5-nitrononane-2,8-dione via sequential biocatalytic reduction steps utilizing ketoreductases to yield all possible diastereomers of 5-nitrononane-2,8-diol. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A biocatalytic cascade with several output signals--towards biosensors with different levels of confidence.

    PubMed

    Guz, Nataliia; Halámek, Jan; Rusling, James F; Katz, Evgeny

    2014-05-01

    The biocatalytic cascade based on enzyme-catalyzed reactions activated by several biomolecular input signals and producing output signal after each reaction step was developed as an example of a logically reversible information processing system. The model system was designed to mimic the operation of concatenated AND logic gates with optically readable output signals generated at each step of the logic operation. Implications include concurrent bioanalyses and data interpretation for medical diagnostics.

  11. A biocatalytic cascade with several output signals—towards biosensors with different levels of confidence

    PubMed Central

    Guz, Nataliia; Halámek, Jan; Rusling, James F.; Katz, Evgeny

    2014-01-01

    The biocatalytic cascade based on enzyme-catalyzed reactions activated by several biomolecular input signals and producing output signal after each reaction step was developed as an example of a logically reversible information processing system. The model system was designed to mimic the operation of concatenated AND logic gates with optically readable output signals generated at each step of the logic operation. Implications include concurrent bioanalyses and data interpretation for medical diagnostics. PMID:24748446

  12. Production of alkenes and novel secondary products by P450 OleTJE using novel H2 O2 -generating fusion protein systems.

    PubMed

    Matthews, Sarah; Tee, Kang Lan; Rattray, Nicholas J; McLean, Kirsty J; Leys, David; Parker, David A; Blankley, Richard T; Munro, Andrew W

    2017-03-01

    Jeotgalicoccus sp. 8456 OleTJE (CYP152L1) is a fatty acid decarboxylase cytochrome P450 that uses hydrogen peroxide (H2 O2 ) to catalyse production of terminal alkenes, which are industrially important chemicals with biofuel applications. We report enzyme fusion systems in which Streptomyces coelicolor alditol oxidase (AldO) is linked to OleTJE . AldO oxidizes polyols (including glycerol), generating H2 O2 as a coproduct and facilitating its use for efficient OleTJE -dependent fatty acid decarboxylation. AldO activity is regulatable by polyol substrate titration, enabling control over H2 O2 supply to minimize oxidative inactivation of OleTJE and prolong activity for increased alkene production. We also use these fusion systems to generate novel products from secondary turnover of 2-OH and 3-OH myristic acid primary products, expanding the catalytic repertoire of OleTJE .

  13. Alkene Metathesis and Renewable Materials: Selective Transformations of Plant Oils

    NASA Astrophysics Data System (ADS)

    Malacea, Raluca; Dixneuf, Pierre H.

    The olefin metathesis of natural oils and fats and their derivatives is the basis of clean catalytic reactions relevant to green chemistry processes and the production of generate useful chemicals from renewable raw materials. Three variants of alkene metathesis: self-metathesis, ethenolysis and cross-metathesis applied to plant oil derivatives will show new routes to fine chemicals, bifunctional products, polymer precursours and industry intermediates.

  14. Nickel-Catalyzed Coupling of Alkenes, Aldehydes, and Silyl Triflates

    PubMed Central

    Ng, Sze-sze; Ho, Chun-Yu; Jamison, Timothy F.

    2011-01-01

    A full account of two recently developed nickel-catalyzed coupling reactions of alkenes, aldehydes and silyl triflates is presented. These reactions provide either allylic alcohol or homoallylic alcohol derivatives selectively, depending on the ligand employed. These processes are believed to be mechanistically distinct from Lewis acid-catalyzed carbonyl-ene reactions, and several lines of evidence supporting this hypothesis are discussed. PMID:16939275

  15. Metal-free syn-dioxygenation of alkenes.

    PubMed

    Rawling, Michael J; Tomkinson, Nicholas C O

    2013-03-07

    Reactions employing inexpensive reagents from sustainable sources and with low toxicity are becoming increasingly desirable from an academic and industrial perspective. A fascinating example of a synthetic transformation that requires development of alternative procedures is the osmium catalysed dihydroxylation. Recently there has been considerable interest in achieving this reaction through metal-free procedures. This review describes the methods available for metal-free syn-dioxygenation of alkenes.

  16. Recent achievements in developing the biocatalytic toolbox for chiral amine synthesis.

    PubMed

    Kohls, Hannes; Steffen-Munsberg, Fabian; Höhne, Matthias

    2014-04-01

    Novel enzyme activities and chemoenzymatic reaction concepts have considerably expanded the biocatalytic toolbox for chiral amine synthesis. Creating new activities or extending the scope of existing enzymes by protein engineering is a common trend in biocatalysis and in chiral amine synthesis specifically. For instance, an amine dehydrogenase that allows for the direct asymmetric amination of ketones with ammonia was created by mutagenesis of an l-amino acid dehydrogenase. Another trend in chiral amine chemistry is the development of strategies allowing for the synthesis of secondary amines. For example the smart choice of substrates for amine transaminases provided access to secondary amines by chemoenzymatic reactions. Furthermore novel biocatalysts for the synthesis of secondary amines such as imine reductases and Pictet-Spenglerases have been identified and applied. Recent examples showed that the biocatalytic amine synthesis is emerging from simple model reactions towards industrial scale preparation of pharmaceutical relevant substances, for instance, as shown in the synthesis of a Janus kinase 2 inhibitor using an amine transaminase. A comparison of important process parameters such as turnover number and space-time yield demonstrates that biocatalytic strategies for asymmetric reductive amination are maturing and can already compete with established chemical methods.

  17. Evaluating the Development of Biocatalytic Technology for the Targeted Removal of Perchlorate from Drinking Water.

    PubMed

    Hutchison, Justin M; Guest, Jeremy S; Zilles, Julie L

    2017-06-20

    Removing micropollutants is challenging in part because of their toxicity at low concentrations. A biocatalytic approach could harness the high affinity of enzymes for their substrates to address this challenge. The potential of biocatalysis relative to mature (nonselective ion exchange, selective ion exchange, and whole-cell biological reduction) and emerging (catalysis) perchlorate-removal technologies was evaluated through a quantitative sustainable design framework, and research objectives were prioritized to advance economic and environmental sustainability. In its current undeveloped state, the biocatalytic technology was approximately 1 order of magnitude higher in cost and environmental impact than nonselective ion exchange. Biocatalyst production was highly correlated with cost and impact. Realistic improvement scenarios targeting biocatalyst yield, biocatalyst immobilization for reuse, and elimination of an electron shuttle could reduce total costs to $0.034 m(-3) and global warming potential (GWP) to 0.051 kg CO2 eq m(-3): roughly 6.5% of cost and 7.3% of GWP of the background from drinking water treatment and competitive with the best performing technology, selective ion exchange. With less stringent perchlorate regulatory limits, ion exchange technologies had increased cost and impact, in contrast to biocatalytic and catalytic technologies. Targeted advances in biocatalysis could provide affordable and sustainable treatment options to protect the public from micropollutants.

  18. Dehydrocyclization of n-octane: Role of alkene intermediates in the reaction mechanism

    SciTech Connect

    Shi, Buchang; Davis, B.H.

    1997-06-01

    The objective of the present study is to define whether alkenes, formed during alkane dehydrocyclization, are reconverted to the alkane and to elucidate the role of alkanes in the dehydrocyclization mechanism. In a competitive conversion, an alkene is converted much more rapidly than n-octane (C{sub 8}D{sub 18}). The lack of H/D exchange indicates that the adsorption of the n-octane is essentially irreversible, whereas some H/D exchange in the added alkene suggests that alkene desorption does occur; however, the added alkene does not desorb as the alkane, in conformity with irreversible adsorption of the alkane. The results demonstrate that the addition of a labeled alkene cannot provide data to establish the validity of the sequential dehydrogenation reaction pathway.

  19. Amine attack on coordinated alkenes: an interconversion from anti-Markovnikoff to Markovnikoff products.

    PubMed

    Pryadun, Ruslan; Sukumaran, Dinesh; Bogadi, Robert; Atwood, Jim D

    2004-10-06

    A sequence of alkene complexes of platinum, PtCl(2)(PPh(3))(alkene) (alkene = ethylene, propene, 1-butene, cis-2-butene, 1-hexene, 1-octene, and 1-decene), has been prepared. These complexes are characterized by NMR spectroscopy, including assignment of each proton, and X-ray crystal structures of the 1-propene and 1-hexene complexes. Each complex was reacted with diethylamine. For the 1-hexene, 1-octene, and 1-decene complexes, the amine displaces the alkene. For the smaller alkenes, the diethylamine nucleophilically attacks the coordinated alkene. For propene and 1-butene, the low-temperature addition leads to the anti-Markovnikoff nucleophilic attack, which slowly converts at room temperature to the Markovnikoff product. The transformation from anti-Markovnikoff to Markovnikoff addition occurs without diethylamine dissociation.

  20. Highly active and efficient catalysts for alkoxycarbonylation of alkenes

    NASA Astrophysics Data System (ADS)

    Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

    2017-01-01

    Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000 TOF: 44,000 h-1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.

  1. Catalytic hydration of terminal alkenes to primary alcohols.

    PubMed

    Jensen, C M; Trogler, W C

    1986-09-05

    Direct catalytic hydration of terminal alkenes to primary alcohols would be an inexpensive route to industrially useful alcohols and a convenient synthetic route for the synthesis of terminal alcohols in general. The reaction between trans- PtHCl(PMe(3))(2) (where Me = CH(3)) and sodium hydroxide in a one-to-one mixture of water and 1-hexene yields a species that, at 60 degrees C and in the presence of the phasetransfer catalyst benzyltriethylammonium chloride, catalyzes selective hydration of 1-hexene to n-hexanol at a rate of 6.9 +/- 0.2 turnovers per hour. Hydration of 1-dodecene to n-dodecanol occurs at a rate of 8.3 +/- 0.4 turnovers per hour at 100 degrees C. Deuterium labeling experiments with trans-PtDCl(PMe(3))(2) show that hydration involves reductive elimination of a C-H bond. At low hydroxide concentrations (<8 equivalents), hydration of the water-soluble olefin 3-butene-1-ol to 1,4-butanediol exhibited a first-order dependence on hydroxide concentration for loss of catalytic activity. This suggests that hydroxide attacks the coordinated alkene slowly. At high hydroxide concentrations, the rate of catalysis was hydroxide-independent and first order in alkene. Substitution of coordinated water (k(1) = 9.3 +/- 0.5 x 10(-3) liters per mol per second) appears to be limitng under these conditions.

  2. Highly active and efficient catalysts for alkoxycarbonylation of alkenes

    PubMed Central

    Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

    2017-01-01

    Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (pytbpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h−1 for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product. PMID:28120947

  3. Highly active and efficient catalysts for alkoxycarbonylation of alkenes.

    PubMed

    Dong, Kaiwu; Fang, Xianjie; Gülak, Samet; Franke, Robert; Spannenberg, Anke; Neumann, Helfried; Jackstell, Ralf; Beller, Matthias

    2017-01-25

    Carbonylation reactions of alkenes constitute the most important industrial processes in homogeneous catalysis. Despite the tremendous progress in this transformation, the development of advanced catalyst systems to improve their activity and widen the range of feedstocks continues to be essential for new practical applications. Herein a palladium catalyst based on 1,2-bis((tert-butyl(pyridin-2-yl)phosphanyl)methyl)benzene L3 (py(t)bpx) is rationally designed and synthesized. Application of this system allows a general alkoxycarbonylation of sterically hindered and demanding olefins including all kinds of tetra-, tri- and 1,1-disubstituted alkenes as well as natural products and pharmaceuticals to the desired esters in excellent yield. Industrially relevant bulk ethylene is functionalized with high activity (TON: >1,425,000; TOF: 44,000 h(-1) for initial 18 h) and selectivity (>99%). Given its generality and efficiency, we expect this catalytic system to immediately impact both the chemical industry and research laboratories by providing a practical synthetic tool for the transformation of nearly any alkene into a versatile ester product.

  4. Biological conversion of gaseous alkenes to liquid chemicals.

    PubMed

    Desai, Shuchi H; Koryakina, Irina; Case, Anna E; Toney, Michael D; Atsumi, Shota

    2016-11-01

    Industrial gas-to-liquid (GTL) technologies are well developed. They generally employ syngas, require complex infrastructure, and need high capital investment to be economically viable. Alternatively, biological conversion has the potential to be more efficient, and easily deployed to remote areas on relatively small scales for the utilization of otherwise stranded resources. The present study demonstrates a novel biological GTL process in which engineered Escherichia coli converts C2-C4 gaseous alkenes into liquid diols. Diols are versatile industrially important chemicals, used routinely as antifreeze agents, polymer precursors amongst many other applications. Heterologous co-expression of a monooxygenase and an epoxide hydrolase in E. coli allows whole cell conversion of C2-C4 alkenes for the formation of ethylene glycol, 1,2-propanediol, 1,2-butanediol, and 2,3-butanediol at ambient temperature and pressure in one pot. Increasing intracellular NADH supply via addition of formate and a formate dehydrogenase increases ethylene glycol production titers, resulting in an improved productivity of 9mg/L/h and a final titer of 250mg/L. This represents a novel biological method for GTL conversion of alkenes to industrially valuable diols.

  5. Copper-catalyzed oxidative carbon-heteroatom bond formation: a recent update.

    PubMed

    Zhu, Xu; Chiba, Shunsuke

    2016-08-08

    This review updates recent advances in Cu-catalyzed (anaerobic) oxidative carbon-heteroatom bond formation on sp(3)- and sp(2)-C-H bonds as well as alkenes, classified according to the types of stoichiometric oxidants.

  6. Efficient alkene hydrogenation over a magnetically recoverable and recyclable Fe3O4@GO nanocatalyst using hydrazine hydrate as the hydrogen source.

    PubMed

    Mondal, John; Nguyen, Kim Truc; Jana, Avijit; Kurniawan, Karina; Borah, Parijat; Zhao, Yanli; Bhaumik, Asim

    2014-10-18

    Magnetic Fe3O4 nanoparticles embedded in graphene oxide (Fe3O4@GO) behave as a highly efficient and reusable heterogeneous nanocatalyst for alkene hydrogenation in EtOH at 80 °C temperature using hydrazine hydrate as the hydrogen source to deliver the corresponding alkanes in good to excellent yields together with high TOF (>4500 h(-1)) within a 4-20 h reaction time.

  7. Efficient epoxidation of a terminal alkene containing allylic hydrogen atoms: trans-methylstyrene on Cu{111}.

    PubMed

    Cropley, Rachael L; Williams, Federico J; Urquhart, Andrew J; Vaughan, Owain P H; Tikhov, Mintcho S; Lambert, Richard M

    2005-04-27

    The selective oxidation of trans-methylstyrene, a phenyl-substituted propene that contains labile allylic hydrogen atoms, has been studied on Cu{111}. Mass spectrometry and synchrotron fast XPS were used to detect, respectively, desorbing gaseous products and the evolution of surface species as a function of temperature and time. Efficient partial oxidation occurs yielding principally the epoxide, and the behavior of the system is sensitive to the order in which reactants are adsorbed. The latter is understandable in terms of differences in the spatial distribution of oxygen adatoms; isolated adatoms lead to epoxidation, while islands of "oxidic" oxygen do not. NEXAFS data taken over a range of coverages and in the presence and absence of coadsorbed oxygen indicate that the adsorbed alkene lies essentially flat with the allylic hydrogen atoms close to the surface. The photoemission results and comparison with the corresponding behavior of styrene on Cu{111} strongly suggest that allylic hydrogen abstraction is indeed a critical factor that limits epoxidation selectivity. An overall mechanism consistent with the structural and reactive properties is proposed.

  8. Regioselective photocycloaddition of pyridine derivatives to electron-rich alkenes.

    PubMed

    Sakamoto, Masami; Sano, Takeru; Fujita, Shohei; Ando, Masaru; Yamaguchi, Kentaro; Mino, Takashi; Fujita, Tsutomu

    2003-02-21

    Irradiation of a benzene solution of 3-cyano-2,6-dimethoxypyridine in the presence of ethyl vinyl ether (EVE) gave 1:1 photoadducts, 3-cyano-5-ethoxy-2,8-dimethoxy-4,5-dihydroazocine, in good yields, whose structure was established by X-ray single-crystal analysis. The photoadduct was produced via cycloaddition between the C3-C4 position of the pyridine derivatives and an alkene chromophore. On the other hand, 3-cyano-2,6-dimethoxy-4-methylpyridine cycloadds to EVE at the C2-C3 position of the pyridine ring upon irradiation. The difference is explained on the basis of the steric effect.

  9. A biocompatible alkene hydrogenation merges organic synthesis with microbial metabolism.

    PubMed

    Sirasani, Gopal; Tong, Liuchuan; Balskus, Emily P

    2014-07-21

    Organic chemists and metabolic engineers use orthogonal technologies to construct essential small molecules such as pharmaceuticals and commodity chemicals. While chemists have leveraged the unique capabilities of biological catalysts for small-molecule production, metabolic engineers have not likewise integrated reactions from organic synthesis with the metabolism of living organisms. Reported herein is a method for alkene hydrogenation which utilizes a palladium catalyst and hydrogen gas generated directly by a living microorganism. This biocompatible transformation, which requires both catalyst and microbe, and can be used on a preparative scale, represents a new strategy for chemical synthesis that combines organic chemistry and metabolic engineering.

  10. Rhodium-catalyzed enantioselective cyclopropanation of electron deficient alkenes

    PubMed Central

    Wang, Hengbin; Guptill, David M.; Alvarez, Adrian Varela

    2013-01-01

    The rhodium-catalyzed reaction of electron-deficient alkenes with substituted aryldiazoacetates and vinyldiazoacetates results in highly stereoselective cyclopropanations. With adamantylglycine derived catalyst Rh2(S-TCPTAD)4, high asymmetric induction (up to 98% ee) can be obtained with a range of substrates. Computational studies suggest that the reaction is facilitated by weak interaction between the carbenoid and the substrate carbonyl but subsequently proceeds via different pathways depending on the nature of the carbonyl.. Acrylates and acrylamides result in the formation of cyclopropanation products while the use of unsaturated aldehydes and ketones results in the formation of epoxides. PMID:24049630

  11. One-pot o-nitrobenzenesulfonylhydrazide (NBSH) formation-diimide alkene reduction protocol.

    PubMed

    Marsh, Barrie J; Carbery, David R

    2009-04-17

    A one-pot protocol for the formation of 2-nitrobenzenesulfonylhydrazide (NBSH) from commercial reagents and subsequent alkene reduction is presented. The transformation is operationally simple and generally efficient for effecting diimide alkene reductions. A range of 16 substrates have been reduced, highlighting the unique chemoselectivity of diimide as a reduction system.

  12. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  13. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  14. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  15. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  16. 40 CFR 721.4464 - Mixture of hydrofluoro alkanes and hydrofluoro alkene.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of hydrofluoro alkanes and... Specific Chemical Substances § 721.4464 Mixture of hydrofluoro alkanes and hydrofluoro alkene. (a) Chemical... as a mixture of hydrofluoro alkanes and hydrofluoro alkene (PMNs P-96-945/946/947/948) are subject...

  17. Hypervalent iodine mediated alkene difunctionalization of vinylphenols: diastereoselective synthesis of substituted indoles and indolizines.

    PubMed

    Zhang, Kai; Wang, Hang; Zheng, Jingfeng; Yu, Lei; Ding, Hanfeng

    2015-04-14

    A hypervalent iodine mediated alkene difunctionalization reaction of vinylphenols has been developed. The chemistry is applicable to a wide range of substitutions on both the alkene and nucleophile substrates, enabling the rapid synthesis of 3-substituted indoles and 2-substituted indolizines in good yields and high diastereoselectivities under metal-free conditions.

  18. Osmium-catalyzed vicinal oxyamination of alkenes by N-(4-toluenesulfonyloxy)carbamates.

    PubMed

    Masruri; Willis, Anthony C; McLeod, Malcolm D

    2012-10-05

    N-(4-toluenesulfonyloxy)carbamates based on a range of common amine protecting groups serve as preformed nitrogen sources in the intermolecular osmium-catalyzed oxyamination reaction of a variety of mono-, di-, and trisubstituted alkenes. The reactions occur with low catalyst loadings and good yields and afford high regioselectivity for unsymmetrically substituted alkenes.

  19. Regioselective hydrothiolation of alkenes bearing heteroatoms with thiols catalyzed by palladium diacetate.

    PubMed

    Tamai, Taichi; Ogawa, Akiya

    2014-06-06

    In sharp contrast to many examples of transition-metal-catalyzed hydrothiolation of alkynes, the corresponding catalytic addition of thiols to alkenes has remained undeveloped. However, a novel Pd-catalyzed addition of thiols to alkenes bearing a heteroatom, such as oxygen and nitrogen, is found to proceed under mild conditions to give the corresponding Markovnikov adducts, regioselectively, in good yields.

  20. Copper-catalyzed intramolecular alkene carboetherification: synthesis of fused-ring and bridged-ring tetrahydrofurans.

    PubMed

    Miller, Yan; Miao, Lei; Hosseini, Azade S; Chemler, Sherry R

    2012-07-25

    Fused-ring and bridged-ring tetrahydrofuran scaffolds are found in a number of natural products and biologically active compounds. A new copper-catalyzed intramolecular carboetherification of alkenes for the synthesis of bicyclic tetrahydrofurans is reported herein. The reaction involves Cu-catalyzed intramolecular addition of alcohols to unactivated alkenes and subsequent aryl C-H functionalization provides the C-C bond. Mechanistic studies indicate a primary carbon radical intermediate is involved and radical addition to the aryl ring is the likely C-C bond-forming mechanism. Preliminary catalytic enantioselective reactions are promising (up to 75% ee) and provide evidence that copper is involved in the alkene addition step, likely through a cis-oxycupration mechanism. Catalytic enantioselective alkene carboetherification reactions are rare and future development of this new method into a highly enantioselective process is promising. During the course of the mechanistic studies a protocol for alkene hydroetherification was also developed.

  1. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C–H Bond Activation

    PubMed Central

    Harada, Hitoshi; Thalji, Reema K.; Bergman, Robert G.; Ellman, Jonathan A.

    2008-01-01

    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe)2]2 and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer. PMID:18681407

  2. Enantioselective Intramolecular Hydroarylation of Alkenes via Directed C-H Bond Activation

    SciTech Connect

    Harada, Hitoshi; Thalji, Reema; Bergman, Robert; Ellman, Jonathan

    2008-05-22

    Highly enantioselective catalytic intramolecular ortho-alkylation of aromatic imines containing alkenyl groups tethered at the meta position relative to the imine directing group has been achieved using [RhCl(coe){sub 2}]{sub 2} and chiral phosphoramidite ligands. Cyclization of substrates containing 1,1- and 1,2-disubstituted as well as trisubstituted alkenes were achieved with enantioselectivities >90% ee for each substrate class. Cyclization of substrates with Z-alkene isomers proceeded much more efficiently than substrates with E-alkene isomers. This further enabled the highly stereoselective intramolecular alkylation of certain substrates containing Z/E-alkene mixtures via a Rh-catalyzed alkene isomerization with preferential cyclization of the Z-isomer.

  3. The alkene monooxygenase from Xanthobacter strain Py2 is closely related to aromatic monooxygenases and catalyzes aromatic monohydroxylation of benzene, toluene, and phenol

    SciTech Connect

    Zhou, N.Y.; Jenkins, A.; Chan Kwo Chion, C.K.N.; Leak, D.J.

    1999-04-01

    The genes encoding the six polypeptide components of the alkene monooxygenase from Xanthobacter strain Py2 (Xamo) have been located on a 4.9-kb fragment of chromosomal DNA previously cloned in cosmid pNY2. Sequencing and analysis of the predicted amino acid sequences indicate that the components of Xamo are homologous to those of the aromatic monooxygenases, toluene 2-, 3-, and 4-monooxygenase and benzene monooxygenase, and that the gene order is identical. The genes and predicted polypeptides are aamA, encoding the 497-residue oxygenase {alpha}-subunit (XamoA); aamB, encoding the 88-residue oxygenase {gamma}-subunit (XamoB); aamC, encoding the 122-residue ferredoxin (XamoC); aamD, encoding the 101-residue coupling or effector protein (XamoD); aamE, encoding the 341-residue oxygenase {beta}-subunit (XamoE); and aamF, encoding the 327-residue reductase (XamoF). A sequence with > 60% concurrence with the consensus sequence of {sigma}{sup 5.4} (RpoN)-dependent promoters was identified upstream of the aamA gene. Detailed comparison of XamoA with the oxygenase {alpha}-subunits from aromatic monooxygenases, phenol hydroxylases, methane monooxygenase, and the alkene monooxygenase from Rhodococcus rhodochrous B276 showed that, despite the overall similarity to the aromatic monooxygenases, XamoA has some distinctive characteristics of the oxygenases which oxidize aliphatic, and particularly alkene, substrates. On the basis of the similarity between Xamo and the aromatic monooxygenases, Xanthobacter strain Py2 was tested and shown to oxidize benzene, toluene, and phenol, while the alkene monooxygenase-negative mutants NZ1 and NZ2 did not.

  4. Bioinformatic analysis of a PLP-dependent enzyme superfamily suitable for biocatalytic applications.

    PubMed

    Steffen-Munsberg, Fabian; Vickers, Clare; Kohls, Hannes; Land, Henrik; Mallin, Hendrik; Nobili, Alberto; Skalden, Lilly; van den Bergh, Tom; Joosten, Henk-Jan; Berglund, Per; Höhne, Matthias; Bornscheuer, Uwe T

    2015-01-01

    In this review we analyse structure/sequence-function relationships for the superfamily of PLP-dependent enzymes with special emphasis on class III transaminases. Amine transaminases are highly important for applications in biocatalysis in the synthesis of chiral amines. In addition, other enzyme activities such as racemases or decarboxylases are also discussed. The substrate scope and the ability to accept chemically different types of substrates are shown to be reflected in conserved patterns of amino acids around the active site. These findings are condensed in a sequence-function matrix, which facilitates annotation and identification of biocatalytically relevant enzymes and protein engineering thereof.

  5. Genes involved in long-chain alkene biosynthesis in Micrococcus luteus

    SciTech Connect

    Beller, Harry R.; Goh, Ee-Been; Keasling, Jay D.

    2010-01-07

    Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which four decades ago was reported to biosynthesize iso- and anteiso branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty-acid overproducing E. coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-CoA produced the same C27 monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or -ACP) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the conserved Cys-His-Asn catalytic triad) of Mlut_13230 (OleA) to FabH (?-ketoacyl-ACP synthase III), which catalyzes decarboxylative Claisen condensation during

  6. Biocatalytic strategies for the asymmetric synthesis of alpha-hydroxy ketones.

    PubMed

    Hoyos, Pilar; Sinisterra, Josep-Vicent; Molinari, Francesco; Alcántara, Andrés R; Domínguez de María, Pablo

    2010-02-16

    The development of efficient syntheses for enantiomerically enriched alpha-hydroxy ketones is an important research focus in the pharmaceutical industry. For example, alpha-hydroxy ketones are found in antidepressants, in selective inhibitors of amyloid-beta protein production (used in the treatment of Alzheimer's), in farnesyl transferase inhibitors (Kurasoin A and B), and in antitumor antibiotics (Olivomycin A and Chromomycin A3). Moreover, alpha-hydroxy ketones are of particular value as fine chemicals because of their utility as building blocks for the production of larger molecules. They can also be used in preparing many other important structures, such as amino alcohols, diols, and so forth. Several purely chemical synthetic approaches have been proposed to afford these compounds, together with some organocatalytic strategies (thiazolium-based carboligations, proline alpha-hydroxylations, and so forth). However, many of these chemical approaches are not straightforward, lack selectivity, or are economically unattractive because of the large number of chemical steps required (usually combined with low enantioselectivities). In this Account, we describe three different biocatalytic approaches that have been developed to efficiently produce alpha-hydroxy ketones: (i) The use of thiamine diphosphate-dependent lyases (ThDP-lyases) to catalyze the umpolung carboligation of aldehydes. Enantiopure alpha-hydroxy ketones are formed from inexpensive aldehydes with this method. Some lyases with a broad substrate spectrum have been successfully characterized. Furthermore, the use of biphasic media with recombinant whole cells overexpressing lyases leads to productivities of approximately 80-100 g/L with high enantiomeric excesses (up to >99%). (ii) The use of hydrolases to produce alpha-hydroxy ketones by means of (in situ) dynamic kinetic resolutions (DKRs). Lipases are able to successfully resolve racemates, and many outstanding examples have been reported. However

  7. Tyramine-based enzymatic conjugate repeats for ultrasensitive immunoassay accompanying tyramine signal amplification with enzymatic biocatalytic precipitation.

    PubMed

    Hou, Li; Tang, Yun; Xu, Mingdi; Gao, Zhuangqiang; Tang, Dianping

    2014-08-19

    A new impedimetric immunoassay protocol based on enzyme-triggered formation of tyramine-enzyme repeats on gold nanoparticle (AuNP) was designed for highly sensitive detection of carcinoembryonic antigen (CEA, as a model) by virtue of utilizing enzymatic biocatalytic precipitation toward 4-chloro-1-naphthol (4-CN) on anti-CEA antibody (Ab1)-modified immunosensor. Initially, AuNP was functionalized with horseradish peroxidase and detection antibody (HRP-AuNP-Ab2), and then HRP-tyramine conjugate was utilized for the formation of tyramine-HRP repeats through the triggering of the immobilized HRP on the AuNP with the aid of H2O2. In the presence of target CEA, the carried HRP-tyramine repeats accompanying the sandwiched immunocomplex catalyzed the 4-CN oxidation to produce an insoluble precipitation on the immunosensor, thus causing a local alteration of the conductivity. Three signal-transduction tags including HRP-Ab2, HRP-AuNP-Ab2, and HRP-AuNP-Ab2 with HRP-tyramine repeats were employed for target CEA evaluation, and improved analytical properties were achieved by HRP-AuNP-Ab2 with HRP-tyramine repeats. Using the unique signal-transduction tag, the analytical performance of the impedimetric immunoassay was studied in detail. Under the optimal conditions, the impedimetric immunosensor displayed a wide dynamic working range of between 0.5 pg mL(-1) and 40 ng mL(-1) with a detection limit (LOD) of 0.38 pg mL(-1) relative to target CEA. The coefficients of variation (CVs) were ≤9.3% and 13.3% for the intra-assay and interassay, respectively. The levels of CEA in eight clinical serum specimens were measured by using the developed impedimetric immunosensor. The obtained results correlated well with those from the electrochemiluminescent (ECL)-based immunoassay with a correlation coefficient of 0.998.

  8. Thermal electron attachment to chlorinated alkenes in the gas phase

    NASA Astrophysics Data System (ADS)

    Wnorowski, K.; Wnorowska, J.; Michalczuk, B.; Jówko, A.; Barszczewska, W.

    2017-01-01

    This paper reports the measurements of the rate coefficients and the activation energies of the electron capture processes with various chlorinated alkenes. The electron attachment processes in the mixtures of chlorinated alkenes with carbon dioxide have been investigated using a Pulsed Townsend technique. This study has been performed in the temperature range (298-378) K. The obtained rate coefficients more or less depended on temperature in accordance to Arrhenius equation. The activation energies (Ea's) were determined from the fit to the experimental data points with function ln(k) = ln(A) - Ea/kBT. The rate coefficients at 298 K were equal to 1.0 × 10-10 cm3 s-1, 2.2 × 10-11 cm3 s-1, 1.6 × 10-9 cm3 s-1, 4.4 × 10-8 cm3 s-1, 2.9 × 10-12 cm3 s-1 and 7.3 × 10-12 cm3 s-1 and activation energies were: 0.27 eV, 0.26 eV, 0.25 eV, 0.21 eV, 0.55 eV and 0.42 eV, for trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, 2-chloropropene, 3-chloropropene respectively.

  9. Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

    PubMed Central

    Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

    2009-01-01

    Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

  10. An osmium(III)/osmium(V) redox couple generating Os(V)(O)(OH) center for cis-1,2-dihydroxylation of alkenes with H2O2: Os complex with a nitrogen-based tetradentate ligand.

    PubMed

    Sugimoto, Hideki; Kitayama, Kazuhiro; Mori, Seiji; Itoh, Shinobu

    2012-11-21

    For the synthesis of the 1,2-diols, cis-1,2-dihydroxylation of alkenes catalyzed by osmium(VIII) tetroxide (OsO(4)) is a powerful method. However, OsO(4) is quite toxic due to its highly volatile and sublimable nature. Thus, the development of alternative catalysts for cis-1,2-dihydroxylation of alkenes is highly challenging. Our approach involves the use of a nitrogen-based tetradentate ligand, tris(2-pyridylmethyl)amine (tpa), for an osmium center to develop a new osmium catalyst and hydrogen peroxide (H(2)O(2)) as a cheap and environmentally benign oxidant. The new Os-tpa complex acts as a very efficient turnover catalyst for syn-selective dihydroxylation of various alkenes (turnover number ∼1000) in aqueous media, and H(2)O(2) oxidant is formally incorporated into the products quantitatively (100% atom efficiency). The reaction intermediates involved in the catalytic cycle have been isolated and characterized crystallographically as [Os(III)(OH)(H(2)O)(tpa)](2+) and [Os(V)(O)(OH)(tpa)](2+) complexes. The observed syn-selectivity, structural characteristics of the intermediates, and kinetic studies have suggested a concerted [3 + 2]-cycloaddition mechanism between [Os(V)(O)(OH)(tpa)](2+) and alkenes, which is strongly supported by DFT calculations.

  11. Reactions of volatile organic compounds in the atmosphere: Ozone-alkene reactions

    NASA Astrophysics Data System (ADS)

    Fenske, Jill Denise

    2000-08-01

    Photochemical smog cannot form without sunlight, nitrogen oxides, and volatile organic compounds (VOC). This dissertation addresses several different aspects of VOC chemistry in the atmosphere. Aside from ambient levels of VOC outdoors, VOC are also present at moderate concentrations indoors. Many studies have measured indoor air concentrations of VOC, but only one considered the effects of human breath. The major VOC in the breath of healthy individuals are isoprene (12-580 ppb), acetone (1.2-1800 ppb), ethanol (13-1000 ppb), methanol (160-2000 ppb), and other alcohols. Human emissions of VOC are negligible on a regional (less than 4%) and global scale (less than 0.3%). However, in indoor air, under fairly crowded situations, human emissions of VOC may dominate other sources of VOC. An important class of VOC in the atmosphere is alkenes, due to their high reactivity. The ozone reaction with alkenes forms OH radicals, a powerful oxidizing agent in the troposphere. OH radical formation yields from the ozonolysis of several cycloalkenes were measured using small amounts of fast-reacting aromatics and aliphatic ethers to trace OH formation. The values are 0.62 +/- 0.15, 0.54 +/- 0.13, 0.36 +/- 0.08, and 0.91 +/- 0.20 for cyclopentene, cyclohexene, cycloheptene and 1-methylcyclohexene, respectively. Density functional theory calculations at the B3LYP/6-31 G(d,p) level are presented to aid in understanding the trends observed. The pressure dependence of OH radical yields may lend insight into the formation mechanism. We have made the first study of the pressure dependence of the OH radical yield for ethene, propene, 1-butene, trans-2-butene, and 2,3-dimethyl-2- butene over the range 20-760 Torr, and trans -3-hexene, and cyclopentene over the range 200-760 Torr. The OH yields from ozonolysis of ethene and propene were pressure dependent, while the other compounds had OH yields that were independent of pressure. Ozone-alkene reactions form vibrationally excited carbonyl

  12. THERMAL REACTIONS OF OXYGEN ATOMS WITH ALKENES AT LOW TEMPERATURES ON INTERSTELLAR DUST

    SciTech Connect

    Ward, Michael D.; Price, Stephen D. E-mail: s.d.price@ucl.ac.uk

    2011-11-10

    Laboratory experiments show that the thermal heterogeneous reactions of oxygen atoms may contribute to the synthesis of epoxides in interstellar clouds. The data set also indicates that the contribution of these pathways to epoxide formation, in comparison to non-thermal routes, is likely to be strongly temperature dependent. Our results indicate that an increased abundance of epoxides, relative to the corresponding aldehydes, could be an observational signature of a significant contribution to molecular oxidation via thermal O atom reactions with alkenes. Specifically surface science experiments show that both C{sub 2}H{sub 4}O and C{sub 3}H{sub 6}O are readily formed from reactions of ethene and propene molecules with thermalized oxygen atoms at temperatures in the range of 12-90 K. It is clear from our experiments that these reactions, on a graphite surface, proceed with significantly reduced reaction barriers compared with those operating in the gas phase. For both the C{sub 2}H{sub 4} + O and the C{sub 3}H{sub 6} + O reactions, the surface reaction barriers we determine are reduced by approximately an order of magnitude compared with the barriers in the gas phase. The modeling of our experimental results, which determines these reaction barriers, also extracts desorption energies and rate coefficients for the title reactions. Our results clearly show that the major product from the O + C{sub 2}H{sub 4} reaction is ethylene oxide, an epoxide.

  13. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    EPA Science Inventory

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  14. Unprecedented Selective Oxidation of Styrene Derivatives using a Supported Iron Oxide Nanocatalyst in Aqueous Medium

    EPA Science Inventory

    Iron oxide nanoparticles supported on mesoporous silica-type materials have been successfully utilized in the aqueous selective oxidation of alkenes under mild conditions using hydrogen peroxide as a green oxidant. Catalysts could be easily recovered after completion of the reac...

  15. Biocatalytic carbon capture via reversible reaction cycle catalyzed by isocitrate dehydrogenase.

    PubMed

    Xia, Shunxiang; Frigo-Vaz, Benjamin; Zhao, Xueyan; Kim, Jungbae; Wang, Ping

    2014-09-12

    The practice of carbon capture and storage (CCS) requires efficient capture and separation of carbon dioxide from its gaseous mixtures such as flue gas, followed by releasing it as a pure gas which can be subsequently compressed and injected into underground storage sites. This has been mostly achieved via reversible thermochemical reactions which are generally energy-intensive. The current work examines a biocatalytic approach for carbon capture using an NADP(H)-dependent isocitrate dehydrogenase (ICDH) which catalyzes reversibly carboxylation and decarboxylation reactions. Different from chemical carbon capture processes that rely on thermal energy to realize purification of carbon dioxide, the biocatalytic strategy utilizes pH to leverage the reaction equilibrium, thereby realizing energy-efficient carbon capture under ambient conditions. Results showed that over 25 mol of carbon dioxide could be captured and purified from its gas mixture for each gram of ICDH applied for each carboxylation/decarboxylation reaction cycle by varying pH between 6 and 9. This work demonstrates the promising potentials of pH-sensitive biocatalysis as a green-chemistry route for carbon capture.

  16. Biocatalytic Synthesis of Allylic and Allenyl Sulfides through a Myoglobin-Catalyzed Doyle-Kirmse Reaction.

    PubMed

    Tyagi, Vikas; Sreenilayam, Gopeekrishnan; Bajaj, Priyanka; Tinoco, Antonio; Fasan, Rudi

    2016-10-17

    The first example of a biocatalytic [2,3]-sigmatropic rearrangement reaction involving allylic sulfides and diazo reagents (Doyle-Kirmse reaction) is reported. Engineered variants of sperm whale myoglobin catalyze this synthetically valuable C-C bond-forming transformation with high efficiency and product conversions across a variety of sulfide substrates (e.g., aryl-, benzyl-, and alkyl-substituted allylic sulfides) and α-diazo esters. Moreover, the scope of this myoglobin-mediated transformation could be extended to the conversion of propargylic sulfides to give substituted allenes. Active-site mutations proved effective in enhancing the catalytic efficiency of the hemoprotein in these reactions as well as modulating the enantioselectivity, resulting in the identification of the myoglobin variant Mb(L29S,H64V,V68F), which is capable of mediating asymmetric Doyle-Kirmse reactions with an enantiomeric excess up to 71 %. This work extends the toolbox of currently available biocatalytic strategies for the asymmetric formation of carbon-carbon bonds.

  17. Biocatalytic virus capsid as nanovehicle for enzymatic activation of Tamoxifen in tumor cells.

    PubMed

    Tapia-Moreno, Alejandro; Juarez-Moreno, Karla; Gonzalez-Davis, Oscar; Cadena-Nava, Ruben D; Vazquez-Duhalt, Rafael

    2017-04-03

    Most of the drugs used in chemotherapy should be activated by a transformation catalyzed by cytochrome P450 (CYP) enzymes. In this work, bacteriophage P22 virus-like particles (VLPs) containing CYP activity, immunologically inert and functionalized in order to be recognized by human cervix carcinoma cells and human breast adenocarcinoma cells were designed. The CYP was encapsulated inside the virus capsid obtained from the bacteriophage P22. CYP and coat protein were both heterologously expressed in E. coli. The VLPs with enzymatic activity were covered with polyethylene glycol that was functionalized in its distal end with folic acid in order to be recognized by folate receptors exhibited on tumor cells. The capacity of biocatalytic VLPs to be recognized and internalized into tumor cells is demonstrated. The VLP-treated cells showed enhanced capacity for the transformation of the pro-drug tamoxifen, which resulted in an increase of the cell sensitivity to this oncological drug. In this work, the potential use of biocatalytic VLPs vehicles as a delivery system of medical relevant enzymes is clearly demonstrated. In addition to cancer treatment, this technology also offers an interesting platform as nano-bioreactors for intracellular delivery of enzymatic activity for other diseases originated by the lack of enzymatic activity.

  18. A robust methodology for kinetic model parameter estimation for biocatalytic reactions.

    PubMed

    Al-Haque, Naweed; Santacoloma, Paloma A; Neto, Watson; Tufvesson, Pär; Gani, Rafiqul; Woodley, John M

    2012-01-01

    Effective estimation of parameters in biocatalytic reaction kinetic expressions are very important when building process models to enable evaluation of process technology options and alternative biocatalysts. The kinetic models used to describe enzyme-catalyzed reactions generally include several parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches. The parameter estimation problem is decomposed into five hierarchical steps, where the solution of each of the steps becomes the input for the subsequent step to achieve the final model with the corresponding regressed parameters. The model is further used for validating its performance and determining the correlation of the parameters. The final model with the fitted parameters is able to describe both initial rate and dynamic experiments. Application of the methodology is illustrated with a case study using the ω-transaminase catalyzed synthesis of 1-phenylethylamine from acetophenone and 2-propylamine.

  19. Rhodium phosphine-π-arene intermediates in the hydroamination of alkenes.

    PubMed

    Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T; Hartwig, John F

    2011-03-02

    A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine is reported. The active catalyst is shown to contain the phosphine ligand bound in a κ(1), η(6) form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C═C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes.

  20. Rhodium Phosphine-π-Arene Intermediates in the Hydroamination of Alkenes

    PubMed Central

    Liu, Zhijian; Yamamichi, Hideaki; Madrahimov, Sherzod T.; Hartwig, John F.

    2011-01-01

    A detailed mechanistic study of the intramolecular hydroamination of alkenes with amines catalyzed by rhodium complexes of a biaryldialkylphosphine are reported. The active catalyst is shown to contain the phosphine ligand bound in a κ1, η6 form in which the arene is π-bound to rhodium. Addition of deuterated amine to an internal olefin showed that the reaction occurs by trans addition of the N-H bond across the C=C bond, and this stereochemistry implies that the reaction occurs by nucleophilic attack of the amine on a coordinated alkene. Indeed, the cationic rhodium fragment binds the alkene over the secondary amine, and the olefin complex was shown to be the catalyst resting state. The reaction was zero-order in substrate, when the concentration of olefin was high, and a primary isotope effect was observed. The primary isotope effect, in combination with the observation of the alkene complex as the resting state, implies that nucleophilic attack of the amine on the alkene is reversible and is followed by turnover-limiting protonation. This mechanism constitutes an unusual pathway for rhodium-catalyzed additions to alkenes and is more closely related to the mechanism for palladium-catalyzed addition of amide N-H bonds to alkenes. PMID:21309512

  1. Environmental significance of biocatalytic conversion of low grade oils

    SciTech Connect

    Lin, M.S.; Premuzic, E.T.; Lian, H.; Zhou, W.M.; Yablon, J.

    1996-09-01

    Studies dealing with the interactions between extremophilic microorganisms and crude oils have led to the identification of biocatalysts which through multiple biochemical reactions catalyze desulfurization, denitrogenation, and demetalation reactions in oils. Concurrently, the oils are also converted to lighter oils. These complex biochemical reactions have served as models in the development of the crude oil bioconversion technology to be applied prior to the treatment of oils by conventional chemical processes. In practical terms, this means that the efficiency of the existing technology is being enhanced. For example, the recently introduced additional regulation for the emission of nitrogen oxides in some states restricts further the kinds of oils that may be used in burners. The biocatalysts being developed in this laboratory selectively interact with nitrogen compounds, i.e. basic and neutral types present in the oil and, hence, affect the fuel NOx production. This, in turn, has a cost-efficient influence on the processed oils and their consumption. In this paper, these cost-efficient and beneficial effects will be discussed in terms of produced oils, the lowering of sulfur and nitrogen contents, and the effect on products, as well as the longevity of catalysts due to the removal of heteroatoms and metal containing compounds found in crudes.

  2. Biocatalytic CO2 sequestration based on shell regeneration

    NASA Astrophysics Data System (ADS)

    Lee, S.

    2012-04-01

    Carbon dioxide, CO2, is one of the green gases, being uniformly distributed over the earth's surface. Recently, a variety of methods exists or has been proposed for pre- or post-emission capture and sequestration of CO2. However, CCS (carbon capture & storage) do not quarntee permanent treatment of CO2 and could ingenerate environment risks. Some organisms convert CO2 into exoskeleton (e.g., mollusks) or energy sources (e.g., plants) during metabolism under atmospheric conditions. One of representative biomaterials in ocean is bivalve shell to be composed of CaCO3. Calcium carbonate is not only abundant material in the world but also thermodynamically stable mineral in the capture of CO2. Bivalve has produced CaCO3 under seawater condition, in other word, near atmospheric conditions (1 atm. and around 20-25 oC). At the inorganic point, the synthesis of CaCO3 is as followed. Ca2+ + CO32- -> CaCO3 The bivalve shell plays an important role to protect bivalve's internal organs from prodetor. What will be happened if the shell is damaged and a hole is made? Bivalve must cover the hole to prevent the oxidation of internal organs as fast as possible. From in vitro crystallization test of a notched shell, rapid CaCO3 production was identified at the damaged area. The biocatalyst related to shell regeneration was purified and named as SPSR (Soluble Protein related to Shell Regeneration) that is obtained from the oyster, Crassostrea gigas. And in vitro CaCO3 crystallization test was used to calculate the crystal growth rate of SPSR on CaCO3 crystallization. The characteristics of SPRR are discussed at the point of CO2 hydration and rapid CaCO3 synthesis. To develop the bioinspired process based on shell regeneration concept, the analysis of protein structure has been studied and the immobilization has been carried out for easy recovery of SPSR.

  3. Selenide-Catalyzed Stereoselective Construction of Tetrasubstituted Trifluoromethylthiolated Alkenes with Alkynes.

    PubMed

    Wu, Jin-Ji; Xu, Jia; Zhao, Xiaodan

    2016-10-17

    The efficient regio- and stereoselective construction of tetrasubstituted alkenes is challenging and very important. For this purpose, we have developed an efficient approach to synthesize tetrasubstituted trifluoromethylthiolated alkenes from simple alkynes in excellent regio- and stereoselectivities by selenide-catalyzed multicomponent coupling. Using this method, trifluoromethylthiolated alkenyl triflates and arenes were achieved. In particular, the triflates could be further converted into carbofunctionalized alkenes by palladium-catalyzed cross-coupling reactions. Our method provides a new pathway for the construction of trifluoromethylthiolated tricarboalkenes. This work presents the first example of selenide-catalyzed trifluoromethylthiolation of alkynes and enables the challenging functionalizations of alkynes.

  4. Catalytic Selenium-Promoted Intermolecular Friedel-Crafts Alkylation with Simple Alkenes.

    PubMed

    Tang, E; Zhao, Yinjiao; Li, Wen; Wang, Weilin; Zhang, Meng; Dai, Xin

    2016-03-04

    A method for conducting selenium-promoted intermolecular Friedel-Crafts (F-C) alkylation reactions has been developed with simple alkenes using trimethylsilyl trifluoromethanesulfonate as a catalyst and N-phenylselenophthalimide as an efficient selenium source. Electron-rich arenes smoothly underwent F-C alkylation with a variety of alkenes to afford alkylated products in good yield and with high regioselectivity and diastereoselectivity. The regioselectivity and stereoselectivity of arenes and alkenes as well as a preliminary mechanism of the F-C alkylation reaction are discussed.

  5. Tandem ring-closing metathesis/transfer hydrogenation: practical chemoselective hydrogenation of alkenes.

    PubMed

    Connolly, Timothy; Wang, Zhongyu; Walker, Michael A; McDonald, Ivar M; Peese, Kevin M

    2014-09-05

    An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.

  6. New developments in gold-catalyzed manipulation of inactivated alkenes

    PubMed Central

    Chiarucci, Michel

    2013-01-01

    Summary Over the recent years, the nucleophilic manipulation of inactivated carbon–carbon double bonds has gained remarkable credit in the chemical community. As a matter of fact, despite lower reactivity with respect to alkynyl and allenyl counterparts, chemical functionalization of isolated alkenes, via carbon- as well as hetero atom-based nucleophiles, would provide direct access to theoretically unlimited added value of molecular motifs. In this context, homogenous [Au(I)] and [Au(III)] catalysis continues to inspire developments within organic synthesis, providing reliable responses to this interrogative, by combining crucial aspects such as chemical selectivity/efficiency with mild reaction parameters. This review intends to summarize the recent progresses in the field, with particular emphasis on mechanistic details. PMID:24367423

  7. Alkene-tetrazine ligation for imaging cellular DNA.

    PubMed

    Rieder, Ulrike; Luedtke, Nathan W

    2014-08-25

    5-Vinyl-2'-deoxyuridine (VdU) is the first reported metabolic probe for cellular DNA synthesis that can be visualized by using an inverse electron demand Diels-Alder reaction with a fluorescent tetrazine. VdU is incorporated by endogenous enzymes into the genomes of replicating cells, where it exhibits reduced genotoxicity compared to 5-ethynyl-2'-deoxyuridine (EdU). The VdU-tetrazine ligation reaction is rapid (k≈0.02 M(-1) s(-1)) and chemically orthogonal to the alkyne-azide "click" reaction of EdU-modified DNA. Alkene-tetrazine ligation reactions provide the first alternative to azide-alkyne click reactions for the bioorthogonal chemical labeling of nucleic acids in cells and facilitate time-resolved, multicolor labeling of DNA synthesis. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Catalytic, Enantioselective Sulfenofunctionalisation of Alkenes: Mechanistic, Crystallographic, and Computational Studies

    PubMed Central

    Denmark, Scott E.; Hartmann, Eduard; Kornfilt, David J. P.; Wang, Hao

    2015-01-01

    The stereocontrolled introduction of vicinal heteroatomic substituents into organic molecules is one of the most powerful ways of adding value and function. Whereas many methods exist for the introduction of oxygen- and nitrogen-containing substituents, the number stereocontrolled methods for the introduction of sulfur-containing substituents pales by comparison. Previous reports from these laboratories have described the sulfenofunctionalization of alkenes that construct vicinal carbon-sulfur and carbon-oxygen, carbon-nitrogen as well as carbon-carbon bonds with high levels of diastereospecificity and enantioselectivity. This process is enabled by the concept of Lewis base activation of Lewis acids that provides activation of Group 16 electrophiles. To provide a foundation for expansion of substrate scope and improved selectivities, we have undertaken a comprehensive study of the catalytically active species. Insights gleaned from kinetic, crystallographic and computational methods have led to the introduction of a new family of sulfenylating agents that provide significantly enhanced selectivities. PMID:25411883

  9. Catalyst system for the polymerization of alkenes to polyolefins

    DOEpatents

    Miller, Stephen A.; Bercaw, John E.

    2002-01-01

    The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.w)in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

  10. Catalyst system for the polymerization of alkenes to polyolefins

    DOEpatents

    Miller, Stephen A.; Bercaw, John E.

    2004-02-17

    The invention provides metallocene catalyst systems for the controlled polymerization of alkenes to a wide variety of polyolefins and olefin coplymers. Catalyst systems are provided that specifically produce isotactic, syndiotactic and steroblock polyolefins. The type of polymer produced can be controlled by varying the catalyst system, specifically by varying the ligand substituents. Such catalyst systems are particularly useful for the polymerization of polypropylene to give elastomeric polypropylenes. The invention also provides novel elastomeric polypropylene polymers characterized by dyad (m) tacticities of about 55% to about 65%, pentad (mmmm) tacticities of about 25% to about 35%, molecular weights (M.sub.W) in the range of about 50,000 to about 2,000,000, and have mmrm+rrmr peak is less than about 5%.

  11. New developments in gold-catalyzed manipulation of inactivated alkenes.

    PubMed

    Chiarucci, Michel; Bandini, Marco

    2013-11-21

    Over the recent years, the nucleophilic manipulation of inactivated carbon-carbon double bonds has gained remarkable credit in the chemical community. As a matter of fact, despite lower reactivity with respect to alkynyl and allenyl counterparts, chemical functionalization of isolated alkenes, via carbon- as well as hetero atom-based nucleophiles, would provide direct access to theoretically unlimited added value of molecular motifs. In this context, homogenous [Au(I)] and [Au(III)] catalysis continues to inspire developments within organic synthesis, providing reliable responses to this interrogative, by combining crucial aspects such as chemical selectivity/efficiency with mild reaction parameters. This review intends to summarize the recent progresses in the field, with particular emphasis on mechanistic details.

  12. Modeling alkene chemistry using condensed mechanisms for conditions relevant to southeast Texas, USA

    NASA Astrophysics Data System (ADS)

    Heo, Gookyoung; Kimura, Yosuke; McDonald-Buller, Elena; Carter, William P. L.; Yarwood, Greg; Allen, David T.

    2010-12-01

    Alkenes are important in photochemical smog formation in southeast Texas due to their high emissions, especially from industrial sources in and around Houston, and their high reactivities. Therefore, properly characterizing the chemistry of alkenes in condensed mechanisms used in regional photochemical models is important in understanding the formation of ozone and other photochemical air pollutants in Houston. The performance of three versions of the SAPRC condensed chemical mechanism family, for predicting ozone and radical formation, was compared. Simulations were compared to environmental chamber data and ambient data. The analyses showed that separately modeling individual alkenes reactions (especially propene for southeast Texas) has the potential to lead to more accurate simulations of alkene chemistry. Caution must be exercised in un-lumping, however. Testing with different formulations of the 1-butene + O 3 reaction demonstrated the complexity and interconnectedness in choices of stoichiometric parameters for un-lumped species and the extent to which lumped mechanisms are un-lumped.

  13. Biobased production of alkanes and alkenes through metabolic engineering of microorganisms.

    PubMed

    Kang, Min-Kyoung; Nielsen, Jens

    2016-08-26

    Advancement in metabolic engineering of microorganisms has enabled bio-based production of a range of chemicals, and such engineered microorganism can be used for sustainable production leading to reduced carbon dioxide emission there. One area that has attained much interest is microbial hydrocarbon biosynthesis, and in particular, alkanes and alkenes are important high-value chemicals as they can be utilized for a broad range of industrial purposes as well as 'drop-in' biofuels. Some microorganisms have the ability to biosynthesize alkanes and alkenes naturally, but their production level is extremely low. Therefore, there have been various attempts to recruit other microbial cell factories for production of alkanes and alkenes by applying metabolic engineering strategies. Here we review different pathways and involved enzymes for alkane and alkene production and discuss bottlenecks and possible solutions to accomplish industrial level production of these chemicals by microbial fermentation.

  14. Asymmetric bioreduction of activated alkenes by a novel isolate of Achromobacter species producing enoate reductase.

    PubMed

    Liu, Yan-Jie; Pei, Xiao-Qiong; Lin, Hui; Gai, Ping; Liu, Yu-Chang; Wu, Zhong-Liu

    2012-08-01

    The strain Achromobacter sp. JA81, which produced enoate reductase, was applied in the asymmetric reduction of activated alkenes. The strain could catalyze the bioreduction of alkenes to form enantiopure (R)-β-aryl-β-cyano-propanoic acids, a precursor of (R)-γ-amino butyric acids, including the pharmaceutically active enantiomer of the chiral drug (R)-baclofen with excellent enantioselectivity. It could catalyze as well the stereoselective bioreduction of other activated alkenes such as cyclic imides, β-nitro acrylates, and nitro-alkenes with up to >99 % ee and >99 % conversion. The draft genome sequencing of JA81 revealed six putative old yellow enzyme homologies, and the transcription of one of them, Achr-OYE3, was detected using reverse transcription polymerase chain reaction. The recombinant Escherichia coli expressing Achr-OYE3 displayed enoate reductase activity toward (Z)-3-cyano-3-phenyl-propenoic acid (2a).

  15. Oxydifluoromethylation of Alkenes by Photoredox Catalysis: Simple Synthesis of CF2H-Containing Alcohols.

    PubMed

    Arai, Yusuke; Tomita, Ren; Ando, Gaku; Koike, Takashi; Akita, Munetaka

    2016-01-22

    We have developed a novel and simple protocol for the direct incorporation of a difluoromethyl (CF2 H) group into alkenes by visible-light-driven photoredox catalysis. The use of fac-[Ir(ppy)3] (ppy=2-pyridylphenyl) photocatalyst and shelf-stable Hu's reagent, N-tosyl-S-difluoromethyl-S-phenylsulfoximine, as a CF2 H source is the key to success. The well-designed photoredox system achieves synthesis of not only β-CF2 H-substituted alcohols but also ethers and an ester from alkenes through solvolytic processes. The present method allows a single-step and regioselective formation of C(sp(3))-CF2 H and C(sp(3))-O bonds from C=C moiety in alkenes, such as hydroxydifluoromethylation, regardless of terminal or internal alkenes. Moreover, this methodology tolerates a variety of functional groups.

  16. Oxydifluoromethylation of Alkenes by Photoredox Catalysis: Simple Synthesis of CF2H‐Containing Alcohols

    PubMed Central

    Arai, Yusuke; Tomita, Ren; Ando, Gaku

    2015-01-01

    Abstract We have developed a novel and simple protocol for the direct incorporation of a difluoromethyl (CF2H) group into alkenes by visible‐light‐driven photoredox catalysis. The use of fac‐[Ir(ppy)3] (ppy=2‐pyridylphenyl) photocatalyst and shelf‐stable Hu's reagent, N‐tosyl‐S‐difluoromethyl‐S‐phenylsulfoximine, as a CF2H source is the key to success. The well‐designed photoredox system achieves synthesis of not only β‐CF2H‐substituted alcohols but also ethers and an ester from alkenes through solvolytic processes. The present method allows a single‐step and regioselective formation of C(sp3)–CF2H and C(sp3)−O bonds from C=C moiety in alkenes, such as hydroxydifluoromethylation, regardless of terminal or internal alkenes. Moreover, this methodology tolerates a variety of functional groups. PMID:26639021

  17. Synthesis of sulfonated oxindoles by potassium iodide catalyzed arylsulfonylation of activated alkenes with sulfonylhydrazides in water.

    PubMed

    Li, Xiaoqing; Xu, Xiangsheng; Hu, Peizhu; Xiao, Xuqiong; Zhou, Can

    2013-07-19

    A catalytic system consisting of KI, 18-crown-6, and TBHP for arylsulfonylation of activated alkenes with sulfonylhydrazides as sulfonyl precursor is described. This protocol provides a practical and environmentally benign method for the construction of sulfonated oxindoles in water.

  18. Is H Atom Abstraction Important in the Reaction of Cl with 1-Alkenes?

    PubMed

    Walavalkar, M P; Vijayakumar, S; Sharma, A; Rajakumar, B; Dhanya, S

    2016-06-23

    The relative yields of products of the reaction of Cl atoms with 1-alkenes (C4-C9) were determined to see whether H atom abstraction is an important channel and if it is to identify the preferred position of abstraction. The presence of all the possible positional isomers of long chain alkenones and alkenols among the products, along with chloroketones and chloroalcohols, confirms the occurrence of H atom abstraction. A consistent pattern of distribution of abstraction products is observed with oxidation at C4 (next to allyl) being the lowest and that at CH2 groups away from the double bond being the highest. This contradicts with the higher stability of allyl (C3) radical. For a better understanding of the relative reactivity, ab initio calculations at MP2/6-311+G (d,p) level of theory are carried out in the case of 1-heptene. The total rate coefficient, calculated using conventional transition state theory, was found to be in good agreement with the experimental value at room temperature. The preferred position of Cl atom addition is predicted to be the terminal carbon atom, which matches with the experimental observation, whereas the rate coefficients calculated for individual channels of H atom abstraction do not explain the observed pattern of products. The distribution of abstraction products except at C4 is found to be better explained by reported structure activity relationship, developed from experimental rate coefficient data. This implies the reactions to be kinetically dictated and emphasizes the importance of secondary reactions.

  19. Fundamental Flame Velocities of Pure Hydrocarbons I : Alkanes, Alkenes, Alkynes Benzene, and Cyclohexane

    NASA Technical Reports Server (NTRS)

    Gerstein, Melvin; Levine, Oscar; Wong, Edgar L

    1950-01-01

    The flame velocities of 37 pure hydrocarbons including normal and branched alkanes, alkenes, and alkynes; as well as benzene and cyclohexane, together with the experimental technique employed are presented. The normal alkanes have about the same flame velocity from ethane through heptane with methane being about 16 percent lower. Unsaturation increases the flame velocity in the order of alkanes, alkenes, and alkynes. Branching reduces the flame velocity.

  20. Copper-catalyzed intermolecular trifluoromethylazidation of alkenes: convenient access to CF3 -containing alkyl azides.

    PubMed

    Wang, Fei; Qi, Xiaoxu; Liang, Zhaoli; Chen, Pinhong; Liu, Guosheng

    2014-02-10

    A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3 -containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3 -containing amine derivatives. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Iminoxyl radical-promoted dichotomous cyclizations: efficient oxyoximation and aminooximation of alkenes.

    PubMed

    Peng, Xie-Xue; Deng, Yun-Jing; Yang, Xiu-Long; Zhang, Lin; Yu, Wei; Han, Bing

    2014-09-05

    A novel iminoxyl radical-involved metal-free approach to vicinal oxyoximation and aminooximation of unactivated alkenes is developed. This method utilizes the dichotomous reactivity of the iminoxyl radical to furnish a general difunctionalization on alkenes using simple tert-butyl nitrite (TBN) as the iminoxyl radical initiator as well the carbon radical trap. By using this protocol, oxime featured 4,5-dihydroisoxazoles and cyclic nitrones were facilely prepared from β,γ- and γ,δ-unsaturated ketoximes, respectively.

  2. Stereochemically Defined Various Multisubstituted Alkenes Bearing a Tetrafluoroethylene (-CF2CF2-) Fragment.

    PubMed

    Sakaguchi, Yukiho; Yamada, Shigeyuki; Konno, Tsutomu; Agou, Tomohiro; Kubota, Toshio

    2017-02-03

    Highly regio- and stereoselective transformation of commercially available 4-bromo-3,3,4,4-tetrafluoro-1-butene into multisubstituted alkenes having a tetrafluoroethylene fragment through Heck reactions and/or Suzuki-Miyaura cross-coupling reactions was established. Thus, the obtained alkenes underwent a smooth reductive coupling reaction with aldehydes under the influence of MeLi/LiBr-free, affording structurally unprecedented fluorinated materials.

  3. Intramolecular azide to alkene cycloadditions for the construction of pyrrolobenzodiazepines and azetidino-benzodiazepines.

    PubMed

    Hemming, Karl; Chambers, Christopher S; Jamshaid, Faisal; O'Gorman, Paul A

    2014-10-17

    The coupling of proline- and azetidinone-substituted alkenes to 2-azidobenzoic and 2-azidobenzenesulfonic acid gives precursors that undergo intramolecular azide to alkene 1,3-dipolar cycloadditions to give imine-, triazoline- or aziridine-containing pyrrolo[1,4]benzodiazepines (PBDs), pyrrolo[1,2,5]benzothiadiazepines (PBTDs), and azetidino[1,4]benzodiazepines. The imines and aziridines are formed after loss of nitrogen from a triazoline cycloadduct. The PBDs are a potent class of antitumour antibiotics.

  4. Quantum Mechanical Study of 10-R-9-Borabicyclo[3.3.2]decane Alkene Hydroboration

    PubMed Central

    Ess, Daniel H.; Kister, Jeremy; Chen, Ming; Roush, William R.

    2009-01-01

    Density functional theory and correlated ab initio quantum mechanical methods were used to locate and analyze alkene hydroboration transition structures for 10-R-9-borabicyclo[3.3.2]decane reagents. Transition-state ensembles quantitatively modeled enantioselectivity for hydroboration of cis-, trans-, and gem-disubstituted alkenes in excellent agreement with experiment. The 10-R group and borabicyclo[3.3.2]decane ring conformation effects were analyzed to understand the origin of asymmetric selectivity. PMID:19824624

  5. Asymmetric Pd-Catalyzed Alkene Carboamination Reactions for the Synthesis of 2-Aminoindane Derivatives.

    PubMed

    White, Derick R; Hutt, Johnathon T; Wolfe, John P

    2015-09-09

    A new type of Pd-catalyzed alkene carboamination reaction that provides direct access to enantioenriched 2-aminoindanes from 2-allylphenyltriflate derivatives and aliphatic amines is described. A catalyst generated in situ from Pd(OAc)2 and (S)-tert-butylPHOX provides the functionalized carbocycles in good yield with up to >99:1 er. The transformations occur via a key anti-aminopalladation that involves intermolecular attack of an amine nucleophile on an arylpalladium alkene complex.

  6. Ruthenium-catalyzed hydroformylation/reduction of olefins to alcohols: extending the scope to internal alkenes.

    PubMed

    Wu, Lipeng; Fleischer, Ivana; Jackstell, Ralf; Profir, Irina; Franke, Robert; Beller, Matthias

    2013-09-25

    In the presence of 2-phosphino-substituted imidazole ligands and Ru3(CO)12 or Ru(methylallyl)2(COD) direct hydroformylation and hydrogenation of alkenes to alcohols takes place. In addition to terminal alkenes, also more challenging internal olefins are converted preferentially to industrially important linear alcohols in high yield (up to 88%) and regioselectivity (n:iso up to 99:1).

  7. Air-Water Interface Effects on the Regioselectivity of Singlet Oxygenations of a Trisubstituted Alkene.

    PubMed

    Malek, Belaid; Ghogare, Ashwini A; Choudhury, Rajib; Greer, Alexander

    2015-07-22

    The regioselective synthesis of allylic hydroperoxide sulfonates by singlet oxygenation at the air-water interface has been found to depend on the concentration of the alkene sulfonate and added calcium salt. The regioselectivity is proposed to originate from an orthogonal alkene relative to the water surface for preferential methyl hydrogen abstraction by airborne singlet oxygen in an ene reaction. The findings hint that the air-water interface is a locale for synthetic reactions.

  8. Heterogeneous allylsilylation of aromatic and aliphatic alkenes catalyzed by proton-exchanged montmorillonite.

    PubMed

    Motokura, Ken; Matsunaga, Shigekazu; Miyaji, Akimitsu; Sakamoto, Yasuharu; Baba, Toshihide

    2010-04-02

    Allylsilylation of an alkene is the only known procedure to install both silyl and allyl groups onto a carbon-carbon double bond directly. Proton-exchanged montmorillonite showed excellent catalytic performances for the allylsilylation of alkenes. For example, the reaction of p-chlorostyrene with allyltrimethylsilane proceeded smoothly to afford the corresponding allylsilylated product in 95% yield. We also attempted to isolate the reaction intermediate on the montmorillonite surface to investigate the reaction mechanism.

  9. Epoxidation of alkenes catalyzed by phenyl group-modified, periodic mesoporous organosilica-entrapped, dimeric manganese-salen complexes.

    PubMed

    Hu, Jianglei; Wu, Qingyin; Li, Wei; Ma, Ling; Su, Fang; Guo, Yihang; Qiu, Yongqing

    2011-12-16

    A series of reusable, recoverable, diamine-bridged dimeric manganese-salen complexes were prepared by the encapsulation of homogeneous dimeric Mn(salen) complexes into nanocages of a 3D periodic mesoporous organosilica (PMO) support followed by silylation of the support with organosilane. The composition, structure, morphology, and textural properties of the prepared PMO-entrapped dimeric Mn(salen) complexes were characterized, and their catalytic performances were tested in the epoxidation of alkenes (styrene, cyclohexene, and 1-phenylcyclohexene), with NaClO as an oxygen source and 4-phenylpyridine-N-oxide as an axial ligand. Furthermore, the influences of the textural and morphological properties of the entrapped dimeric Mn(salen) complexes and the key reaction parameters on the catalytic activity and selectivity are discussed. Finally, the reusability of the supported dimeric Mn(salen) complexes was evaluated over three catalytic runs.

  10. Products and Mechanisms of Aerosol Formation from Reactions of OH Radicals with Linear and Branched Alkenes in the Presence of NOx (Invited)

    NASA Astrophysics Data System (ADS)

    Ziemann, P. J.; Matsunaga, A.

    2009-12-01

    The chemical and physical processes involved in the formation of secondary organic aerosol (SOA) are complex and can include reactions of volatile organic compounds with a number of atmospheric oxidants (the major ones are O3, and OH and NO3 radicals), as well as surface and condensed-phase reactions, homogeneous nucleation, and gas-particle partitioning. It should come as no surprise that understanding and accurately modeling these processes is a major challenge that has not yet been fully addressed. Alkenes emitted from vegetation are the largest source of non-methane hydrocarbons to the global atmosphere and consist mostly of isoprene (C5H8), monoterpenes (C10H16), and sesquiterpenes (C15H24), compounds with a large range of sizes and molecular structures. Their atmospheric oxidation is initiated primarily by reactions with hydroxyl radicals and can lead to a variety of products, some of which can form SOA. Because of the complexity of terpene reactions and the large numbers of products that are formed, there are advantages to studying the chemistry of simpler alkenes in order to gain insights that can be applied to more complex reaction systems. This is the approach we have taken, and in this talk I will report results of studies of the products, SOA yields, and mechanisms of SOA formation from reactions of a variety of linear and branched alkenes with hydroxyl radicals in the presence of nitrogen oxides. Products consist of a large array of multifunctional compounds, including oligomers, containing carbonyl, hydroxy, carboxyl, and nitrate groups. I will demonstrate some of the ways in which changes in molecular structure can alter both gas and SOA products, including those formed through condensed-phase reactions, and also SOA yields, and suggest explanations for these effects based on current understanding of chemical reaction mechanisms.

  11. Bubble-Free Propulsion of Ultrasmall Tubular Nanojets Powered by Biocatalytic Reactions.

    PubMed

    Ma, Xing; Hortelao, Ana C; Miguel-López, Albert; Sánchez, Samuel

    2016-10-26

    The motion of self-propelled tubular micro- and nanojets has so far been achieved by bubble propulsion, e.g., O2 bubbles formed by catalytic decomposition of H2O2, which renders future biomedical applications inviable. An alternative self-propulsion mechanism for tubular engines on the nanometer scale is still missing. Here, we report the fabrication and characterization of bubble-free propelled tubular nanojets (as small as 220 nm diameter), powered by an enzyme-triggered biocatalytic reaction using urea as fuel. We studied the translational and rotational dynamics of the nanojets as functions of the length and location of the enzymes. Introducing tracer nanoparticles into the system, we demonstrated the presence of an internal flow that extends into the external fluid via the cavity opening, leading to the self-propulsion. One-dimensional nanosize, longitudinal self-propulsion, and biocompatibility make the tubular nanojets promising for future biomedical applications.

  12. Chemotherapy pro-drug activation by biocatalytic virus-like nanoparticles containing cytochrome P450.

    PubMed

    Sánchez-Sánchez, Lorena; Cadena-Nava, Rubén D; Palomares, Laura A; Ruiz-Garcia, Jaime; Koay, Melissa S T; Cornelissen, Jeroen J M T; Vazquez-Duhalt, Rafael

    2014-06-10

    This work shows, for the first time, the encapsulation of a highly relevant protein in the biomedical field into virus-like particles (VLPs). A bacterial CYP variant was effectively encapsulated in VLPs constituted of coat protein from cowpea chlorotic mottle virus (CCMV). The catalytic VLPs are able to transform the chemotherapeutic pro-drug, tamoxifen, and the emerging pro-drug resveratrol. The chemical nature of the products was identified, confirming similar active products than those obtained with human CYP. The enzymatic VLPs remain stable after the catalytic reaction. The potential use of these biocatalytic nanoparticles as targeted CYP carriers for the activation of chemotherapy drugs is discussed. Copyright © 2014 Elsevier Inc. All rights reserved.

  13. Biocatalytic self-assembly of nanostructured peptide microparticles using droplet microfluidics.

    PubMed

    Bai, Shuo; Debnath, Sisir; Gibson, Kirsty; Schlicht, Barbara; Bayne, Lauren; Zagnoni, Michele; Ulijn, Rein V

    2014-01-29

    Uniformly-sized, nanostructured peptide microparticles are generated by exploiting the ability of enzymes to serve (i) as catalysts, to control self-assembly within monodisperse, surfactant-stabilized water-in-oil microdroplets, and (ii) as destabilizers of emulsion interfaces, to enable facile transfer of the produced microparticles to water. This approach combines the advantages of biocatalytic self-assembly with the compartmentalization properties enabled by droplet microfluidics. Firstly, using microfluidic techniques, precursors of self-assembling peptide derivatives and enzymes are mixed in the microdroplets which upon catalytic conversion undergo molecular self-assembly into peptide particles, depending on the chemical nature of the precursors. Due to their amphiphilic nature, enzymes adsorb at the water-surfactant-oil interface of the droplets, inducing the transfer of peptide microparticles from the oil to the aqueous phase. Ultimately, through washing steps, enzymes can be removed from the microparticles which results in uniformely-sized particles composed of nanostructured aromatic peptide amphiphiles.

  14. Bubble-Free Propulsion of Ultrasmall Tubular Nanojets Powered by Biocatalytic Reactions

    PubMed Central

    2016-01-01

    The motion of self-propelled tubular micro- and nanojets has so far been achieved by bubble propulsion, e.g., O2 bubbles formed by catalytic decomposition of H2O2, which renders future biomedical applications inviable. An alternative self-propulsion mechanism for tubular engines on the nanometer scale is still missing. Here, we report the fabrication and characterization of bubble-free propelled tubular nanojets (as small as 220 nm diameter), powered by an enzyme-triggered biocatalytic reaction using urea as fuel. We studied the translational and rotational dynamics of the nanojets as functions of the length and location of the enzymes. Introducing tracer nanoparticles into the system, we demonstrated the presence of an internal flow that extends into the external fluid via the cavity opening, leading to the self-propulsion. One-dimensional nanosize, longitudinal self-propulsion, and biocompatibility make the tubular nanojets promising for future biomedical applications. PMID:27718566

  15. Biocatalytic asymmetric synthesis of chiral amines from ketones applied to sitagliptin manufacture.

    PubMed

    Savile, Christopher K; Janey, Jacob M; Mundorff, Emily C; Moore, Jeffrey C; Tam, Sarena; Jarvis, William R; Colbeck, Jeffrey C; Krebber, Anke; Fleitz, Fred J; Brands, Jos; Devine, Paul N; Huisman, Gjalt W; Hughes, Gregory J

    2010-07-16

    Pharmaceutical synthesis can benefit greatly from the selectivity gains associated with enzymatic catalysis. Here, we report an efficient biocatalytic process to replace a recently implemented rhodium-catalyzed asymmetric enamine hydrogenation for the large-scale manufacture of the antidiabetic compound sitagliptin. Starting from an enzyme that had the catalytic machinery to perform the desired chemistry but lacked any activity toward the prositagliptin ketone, we applied a substrate walking, modeling, and mutation approach to create a transaminase with marginal activity for the synthesis of the chiral amine; this variant was then further engineered via directed evolution for practical application in a manufacturing setting. The resultant biocatalysts showed broad applicability toward the synthesis of chiral amines that previously were accessible only via resolution. This work underscores the maturation of biocatalysis to enable efficient, economical, and environmentally benign processes for the manufacture of pharmaceuticals.

  16. Biocatalytic synthesis of acrylates in supercritical fluids: tuning enzyme activity by changing pressure.

    PubMed Central

    Kamat, S V; Iwaskewycz, B; Beckman, E J; Russell, A J

    1993-01-01

    Supercritical fluids are a unique class of nonaqueous media in which biocatalytic reactions can occur. The physical properties of supercritical fluids, which include gas-like diffusivities and liquid-like densities, can be predictably controlled with changing pressure. This paper describes how adjustment of pressure, with the subsequent predictable changes of the dielectric constant and Hildebrand solubility parameter for fluoroform, ethane, sulfur hexafluoride, and propane, can be used to manipulate the activity of lipase in the transesterification of methylmethacrylate with 2-ethyl-1-hexanol. Of particular interest is that the dielectric constant of supercritical fluoroform can be tuned from approximately 1 to 8, merely by increasing pressure from 850 to 4000 psi (from 5.9 to 28 MPa). The possibility now exists to predictably alter both the selectivity and the activity of a biocatalyst merely by changing pressure. Images Fig. 6 PMID:8464910

  17. One-pot, single-step deracemization of 2-hydroxyacids by tandem biocatalytic oxidation and reduction.

    PubMed

    Xue, Ya-Ping; Zheng, Yu-Guo; Zhang, Ya-Qin; Sun, Jing-Lei; Liu, Zhi-Qiang; Shen, Yin-Chu

    2013-11-25

    A facile and efficient one-pot, single-step method for deracemizing a broad range of 2-hydroxyacids to (R)-2-hydroxyacids was established by combination of resting cells of an (S)-hydroxyacid dehydrogenase-producing microorganism and an (R)-ketoacid reductase-producing microorganism.

  18. Well-Defined Polymers Bearing Pendent Alkene Functionalities via Selective RAFT Polymerization

    PubMed Central

    Ma, Jun; Cheng, Chong; Sun, Guorong; Wooley, Karen L.

    2009-01-01

    A facile synthetic approach for the preparation of well-defined (co)polymers bearing pendent alkene functionalities was established by selective reversible addition-fragmentation chain transfer (RAFT) (co)polymerization. A divinyl monomer 4-(3′-buten-1′-oxy)-2,3,5,6-tetrafluorostyrene (1) with a styrenyl group and a pendent alkene group was synthesized. Due to a very high reactivity of the styrenyl group relative to the alkene group in 1, functional fluoro(co)polymers with both well-defined structures and pendent alkene groups were prepared by RAFT polymerizations of 1 and copolymerization of 1 with pentafluorostyrene (PFS). Alkene-functionalized diblock copolymers were also prepared by RAFT copolymerization of 1 with PFS or styrene, extending from a poly(styrene-alt-maleic anhydride) macro-chain transfer agent. Hydrolysis and ammonolysis of these copolymers resulted in amphiphilic diblock fluorocopolymers with alkene-functionalized hydrophobic segments, which were shown to form internally-functionalized micelles in THF-water. PMID:20640195

  19. Direct kinetic measurements of reactions between the simplest Criegee intermediate CH2OO and alkenes.

    PubMed

    Buras, Zachary J; Elsamra, Rehab M I; Jalan, Amrit; Middaugh, Joshua E; Green, William H

    2014-03-20

    The simplest Criegee Intermediate (CH2OO), a well-known biradical formed in alkene ozonolysis, is known to add across double bonds. Here we report direct experimental rate measurements of the simplest Criegee Intermediate reacting with C2–C4 alkenes obtained using the laser flash photolysis technique probing the recently measured B(1)A′ ← X(1)A′ transition in CH2OO. The measured activation energy (298–494 K) for CH2OO + alkenes is Ea ≈ 3500 ± 1000 J mol(–1) for all alkyl substituted alkenes and Ea = 7000 ± 900 J mol(–1) for ethene. The measured Arrhenius pre-exponential factors (A) vary between (2 ± 1) × 10(–15) and (11 ± 3) × 10(–15) cm(3) molecule(–1) s(–1). Quantum chemical calculations of the corresponding rate coefficients reproduce qualitative reactivity trends but overestimate the absolute rate coefficients. Despite the small Ea's, the CH2OO + alkene rate coefficients are almost 2 orders of magnitude smaller than those of similar reactions between CH2OO and carbonyl compounds. Using the rate constants measured here, we estimate that, under typical atmospheric conditions, reaction with alkenes does not represent a significant sink of CH2OO. In environments rich in C═C double bonds, however, such as ozone-exposed rubber or emission plumes, these reactions can play a significant role.

  20. Exploiting Natural Variation to Uncover an Alkene Biosynthetic Enzyme in Poplar[OPEN

    PubMed Central

    La Mantia, Jonathan

    2017-01-01

    Alkenes are linear hydrocarbons with one or more double bonds. Despite their potential as biofuels and precursors for specialty chemicals, the underlying biochemistry and genetics of alkene biosynthesis in plants remain elusive. Here, we report on a screen of natural accessions of poplar (Populus trichocarpa), revealing that the leaf cuticular waxes are predominantly composed of alkanes and alkenes. Interestingly, the accumulation of alkenes increases with leaf development, is limited to the abaxial side of the leaf, and is impaired in a few accessions. Among other genes, a β-ketoacyl CoA synthase gene (PotriKCS1) was downregulated in leaves from non-alkene-producing accessions. We demonstrated biochemically that PotriKCS1 elongates monounsaturated fatty acids and is responsible for the recruitment of unsaturated substrates to the cuticular wax. Moreover, we found significant associations between the presence of alkenes and tree growth and resistance to leaf spot. These findings highlight the crucial role of cuticular waxes as the first point of contact with the environment, and they provide a foundation for engineering long-chain monounsaturated oils in other species. PMID:28729404

  1. Regioselective Oxo-Amination of Alkenes and Enol Ethers with N-Bromosuccinimide-Dimethyl Sulfoxide Combination: A Facile Synthesis of α-Amino-Ketones and Esters.

    PubMed

    Prasad, Pragati K; Reddi, Rambabu N; Sudalai, Arumugam

    2016-02-05

    An unprecedented conversion of alkenes and enol ethers to the corresponding α-imido carbonyl compounds with excellent regioselectivity and yields has been developed. This oxo-amination process employs readily available N-bromosuccinimide (NBS) and secondary amines as N-sources and dimethyl sulfoxide (DMSO) as the oxidant and also leads to the production of amino alcohols in a single step on reduction, thus broadening the scope of this operationally simple reaction. For the first time, the formation of reactive Me2S(+)-O-Br species generated by the interaction of NBS with DMSO has been proven.

  2. Selective thermal oxidation of hydrocarbons in zeolites by oxygen

    DOEpatents

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    2000-01-01

    A process for selective thermal oxidation of hydrocarbons adsorbed onto zeolite matrices. A highly selective thermal oxidation of unsubstituted or alkyl substituted alkanes, alkenes, aromatics and cycloalkyls is carried out in solvent free zeolites under dark thermal conditions. The process oxidizes hydrocarbons almost completely selectively without substantial production of byproducts.

  3. Genes involved in long-chain alkene biosynthesis in Micrococcus luteus.

    PubMed

    Beller, Harry R; Goh, Ee-Been; Keasling, Jay D

    2010-02-01

    Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which 4 decades ago was reported to biosynthesize iso- and anteiso-branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty acid-overproducing Escherichia coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-coenzyme A (CoA) produced the same C(27) monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or-ACP [acyl carrier protein]) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the conserved Cys-His-Asn catalytic triad) of Mlut_13230 (OleA) to FabH (beta-ketoacyl-ACP synthase III), which

  4. Genes Involved in Long-Chain Alkene Biosynthesis in Micrococcus luteus▿

    PubMed Central

    Beller, Harry R.; Goh, Ee-Been; Keasling, Jay D.

    2010-01-01

    Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which 4 decades ago was reported to biosynthesize iso- and anteiso-branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty acid-overproducing Escherichia coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C 000000000000 000000000000 000000000000 111111111111 000000000000 111111111111 000000000000 000000000000 000000000000 C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-coenzyme A (CoA) produced the same C27 monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or-ACP [acyl carrier protein]) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the

  5. Mechanistic interpretation of selective catalytic hydrogenation and isomerization of alkenes and dienes by ligand deactivated Pd nanoparticles.

    PubMed

    Zhu, Jie S; Shon, Young-Seok

    2015-11-14

    Unsupported thiolate-capped palladium nanoparticle catalysts are found to be highly substrate-selective for alkene hydrogenation and isomerization. Steric and poisoning effects from thiolate ligands on the nanoparticle surface control reactivity and selectivity by influencing alkene adsorption and directing either di-σ or mono-σ bond formation. The presence of overlapping p orbitals and α protons in alkenes greatly influences the catalytic properties of deactivated palladium nanoparticles leading to easily predictable hydrogenation or isomerization products.

  6. Imaging the dynamics of chlorine atom reactions with alkenes

    NASA Astrophysics Data System (ADS)

    Estillore, Armando D.; Visger, Laura M.; Suits, Arthur G.

    2010-08-01

    We report a study of chlorine atom reactions with a series of target monounsaturated alkene molecules: 1-pentene, 1-hexene, 2-hexene, and cyclohexene. These reactions were studied using crossed-beam dc slice ion imaging at collision energies of 4 and 7 kcal/mol. Images of the reactively scattered alkenyl radical products were obtained via single photon ionization at 157 nm. The angular distributions at low collision energy are largely isotropic, suggesting the formation of a complex that has a lifetime comparable to or longer than its rotational period, followed by HCl elimination. At high collision energy, the distributions show a sharp forward peak superimposed on the isotropic component accounting for ˜13% of the product flux. The translational energy distributions peak near zero for the backscattered product, in sharp contrast to the results for alkanes. In the forward direction, the translational energy distributions change dramatically with collision energy. At the high collision energy, a sharp forward peak at ˜80% of the collision energy appears, quite reminiscent of results of our recent study of Cl+pentane reactions. The scattering distributions for all target molecules are similar, suggesting similarity of the reaction dynamics among these molecules. Ab initio calculations of the energetics and ionization energies for the various product channels were performed at the CBS-QB3 level to aid in interpreting the results.

  7. Kinetics of the polymerization of alkenes on zeolites

    NASA Astrophysics Data System (ADS)

    Alberty, Robert A.

    1987-09-01

    The polymerization of alkenes at temperatures in the neighborhood of 600 K on a zeolite catalyst can be described in terms of a mechanism with bimolecular polymerization reactions and cracking reactions of isomer groups. The rate equations for the formation of isomer groups up to C13H26 have been integrated using the fourth-order Runge-Kutta method for polymerizations at constant temperature and pressure. In the absence of data on rate constants, calculations have been made on the basis of the assumption that all the bimolecular rate constants are equal or all the cracking constants are equal. In each case the rate constants for the reverse reactions have been calculated using the equilibrium constants for the steps in the mechanism. Under some circumstances the plots of weight fractions of isomer groups vs time have nearly the same shape for the two assumptions. However, it is possible to distinguish between the two assumptions by using experiments at sufficiently high pressures. The calculations show that it is of interest to examine the compositions arising from different starting materials, even though the equilibrium composition depends only upon temperature and pressure.

  8. Rational Improvement of Simvastatin Synthase Solubility in Escherichia coli Leads to Higher Whole-cell Biocatalytic Activity

    PubMed Central

    Xie, Xinkai; Pashkov, Inna; Gao, Xue; Guerrero, Jennifer L.; Yeates, Todd O.; Tang, Yi

    2014-01-01

    Simvastatin is the active pharmaceutical ingredient of the blockbuster cholesterol lowering drug Zocor. We have previously developed an Escherichia coli based whole-cell biocatalytic platform towards the synthesis of simvastatin sodium salt (SS) starting from the precursor monacolin J sodium salt (MJSS). The centerpiece of the biocatalytic approach is the simvastatin synthase LovD, which is highly prone to misfolding and aggregation when overexpressed from E. coli. Increasing the solubility of LovD without decreasing its catalytic activity can therefore elevate the performance of the whole-cell biocatalyst. Using a combination of homology structural prediction and site-directed mutagenesis, we identified two cysteine residues in LovD that are responsible for nonspecific intermolecular crosslinking, which leads to oligomer formation and protein aggregation. Replacement of Cys40 and Cys60 with alanine residues resulted in marked gain in both protein solubility and whole-cell biocatalytic activities. Further mutagenesis experiments converting these two residues to small or polar natural amino acids showed that C40A and C60N are the most beneficial, affording 27% and 26% increase in whole cell activities, respectively. The double mutant C40A/C60N combines the individual improvements and displayed ~50% increase in protein solubility and whole-cell activity. Optimized fed-batch high-cell-density fermentation of the double mutant in an E. coli strain engineered for simvastatin production quantitatively (>99%) converted 45 mM MJSS to SS within 18 hours, which represents a significant improvement over the performance of wild type LovD under identical conditions. The high efficiency of the improved whole-cell platform renders the biocatalytic synthesis of SS an attractive substitute over the existing semisynthetic routes. PMID:18988191

  9. Pressure dependence of stabilized Criegee intermediate formation from a sequence of alkenes.

    PubMed

    Drozd, Greg T; Donahue, Neil M

    2011-05-05

    Ozonolysis is a key reaction in atmospheric chemistry, although important details of the behavior of the ozonolysis intermediates are not known. The key intermediate in ozonolysis, the Criegee intermeiate (CI), is known to quickly isomerize, with the favored unimolecular pathway depending on the relative barriers to isomerization. Stabilized Criegee intermediates (SCI), those with energy below any barriers to isomerization, may result from initial formation with low energy or collisional stabilization of high energy CI. Bimolecular reactions of SCI have been proposed to play a role in OH formation and nucleation of new particles, but unimolecular reactions of SCI may well be too fast for these to be significant. We present measurements of the pressure dependence of SCI formation for a set of alkenes utilizing a hexafluoroacetone scavenger. We studied four alkenes (2,3-dimethyl-2-butene (TME), trans-5-decene, cyclohexene, α-pinene) to characterize how size and cyclization (endo vs exo) affect the stability of Criegee intermediates formed in ozonolysis. SCI yields in ozonolysis were measured in a high pressure flow reactor within a range of 30-750 Torr. The linear alkenes show considerable stabilization with trans-5-decene showing 100% stabilization at ∼400 Torr and TME having 65% stabilization at 710 Torr. Extrapolation of the yields for linear alkenes to 0 Torr shows yields significantly above zero, indicating that a fraction of their CI are formed below the barrier to isomerization. CI from endocyclic alkenes show little to no stabilization and appear to have neglible stabilization at 0 Torr. Cyclohexene derived CI showed no stabilization even at 650 Torr, while α-pinene CI had ∼15% stabilization at 740 Torr. Our results show a strong dependence of SCI formation on carbon number; adding just 2 to 3 CI carbons in linear alkenes increases stabilization by a factor of 10. Stabilization for endocyclic alkenes, at atmospheric pressure, begins to occur at a carbon

  10. Electro-biocatalytic production of formate from carbon dioxide using an oxygen-stable whole cell biocatalyst.

    PubMed

    Hwang, Hyojin; Yeon, Young Joo; Lee, Sumi; Choe, Hyunjun; Jang, Min Gee; Cho, Dae Haeng; Park, Sehkyu; Kim, Yong Hwan

    2015-06-01

    The use of biocatalysts to convert CO2 into useful chemicals is a promising alternative to chemical conversion. In this study, the electro-biocatalytic conversion of CO2 to formate was attempted with a whole cell biocatalyst. Eight species of Methylobacteria were tested for CO2 reduction, and one of them, Methylobacterium extorquens AM1, exhibited an exceptionally higher capability to synthesize formate from CO2 by supplying electrons with electrodes, which produced formate concentrations of up to 60mM. The oxygen stability of the biocatalyst was investigated, and the results indicated that the whole cell catalyst still exhibited CO2 reduction activity even after being exposed to oxygen gas. From the results, we could demonstrate the electro-biocatalytic conversion of CO2 to formate using an obligate aerobe, M. extorquens AM1, as a whole cell biocatalyst without providing extra cofactors or hydrogen gas. This electro-biocatalytic process suggests a promising approach toward feasible way of CO2 conversion to formate. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Evaluation of performance and stability of biocatalytic redox films constructed with different copper oxygenases and osmium-based redox polymers.

    PubMed

    Jenkins, Peter A; Boland, Susan; Kavanagh, Paul; Leech, Dónal

    2009-09-01

    We are interested in investigating the applications of biocatalytic mediated reduction of oxygen by oxygenases in films on electrode surfaces, as such reactions can form the basis for biosensors or biocatalytic fuel cell development. Here we present approaches aimed at improving the stability and signal output of such films. These include selection of oxygen reducing biocatalysts which are active under physiological conditions and development of redox mediators which offer the opportunity to tailor the mediator to each enzyme. It was found that for each enzyme Melanocarpus albomyces laccase (MaL), Trametes hirsutus laccase (ThL) or bilirubin oxidase (MvBOD) it was the biocatalytic films mediated by Os(2,2'-bipyridine)(2)Cl.PVI that not only generated the highest current densities compared to Os(4,4'-dimethyl-2,2'-bipyridine)(2)Cl.PVI and Os(4,4'-dichloro-2,2'-bipyridine)(2)Cl.PVI, but also proved to be the most stable over 48 h. Under physiological conditions electrodes constructed from MvBOD generated the highest initial current densities for each of the osmium redox polymers, however these films proved to be the least stable over 48 h. Stability could be improved using surface pre-treatment.

  12. Use of a Ceramic Membrane to Improve the Performance of Two-Separate-Phase Biocatalytic Membrane Reactor.

    PubMed

    Ranieri, Giuseppe; Mazzei, Rosalinda; Wu, Zhentao; Li, Kang; Giorno, Lidietta

    2016-03-14

    Biocatalytic membrane reactors (BMR) combining reaction and separation within the same unit have many advantages over conventional reactor designs. Ceramic membranes are an attractive alternative to polymeric membranes in membrane biotechnology due to their high chemical, thermal and mechanical resistance. Another important use is their potential application in a biphasic membrane system, where support solvent resistance is highly needed. In this work, the preparation of asymmetric ceramic hollow fibre membranes and their use in a two-separate-phase biocatalytic membrane reactor will be described. The asymmetric ceramic hollow fibre membranes were prepared using a combined phase inversion and sintering technique. The prepared fibres were then used as support for lipase covalent immobilization in order to develop a two-separate-phase biocatalytic membrane reactor. A functionalization method was proposed in order to increase the density of the reactive hydroxyl groups on the surface of ceramic membranes, which were then amino-activated and treated with a crosslinker. The performance and the stability of the immobilized lipase were investigated as a function of the amount of the immobilized biocatalytst. Results showed that it is possible to immobilize lipase on a ceramic membrane without altering its catalytic performance (initial residual specific activity 93%), which remains constant after 6 reaction cycles.

  13. Biocatalytic polymer coatings: on-demand drug synthesis and localized therapeutic effect under dynamic cell culture conditions.

    PubMed

    Fejerskov, Betina; Jensen, Najah B S; Teo, Boon M; Städler, Brigitte; Zelikin, Alexander N

    2014-04-09

    Biocatalytic surface coatings are prepared herein for localized synthesis of drugs and their on-demand, site-specific delivery to adhering cells. This novel approach is based on the incorporation of an enzyme into multilayered polymer coatings to accomplish enzyme-prodrug therapy (EPT). The build-up of enzyme-containing multilayered coatings is characterized and correlations are drawn between the multilayer film assembly conditions and the enzymatic activity of the resulting coatings. Therapeutic effect elicited by the substrate mediated EPT (SMEPT) strategy is investigated using a prodrug for an anticancer agent, SN-38. The performance of biocatalytic coatings under flow conditions is investigated and it is demonstrated that EPT allows synthesizing the drugs on-demand, at the time desired and in a controllable amount to suit particular applications. Finally, using cells cultured in sequentially connected flow chambers, it is demonstrated that SMEPT affords a site-specific drug delivery, that is, exerts a higher therapeutic effect in cells adhering directly to the biocatalytic coatings than in the cells cultured "downstream". Taken together, these data illustrate biomedical opportunities made possible by engineering tools of EPT into multilayered polymer coatings and present a novel, highly versatile tool for surface mediated drug delivery.

  14. Efficiency Analysis and Mechanism Insight of that Whole-Cell Biocatalytic Production of Melibiose from Raffinose with Saccharomyces cerevisiae.

    PubMed

    Zhou, Yingbiao; Zhu, Yueming; Dai, Longhai; Men, Yan; Wu, Jinhai; Zhang, Juankun; Sun, Yuanxia

    2017-01-01

    Melibiose is widely used as a functional carbohydrate. Whole-cell biocatalytic production of melibiose from raffinose could reduce its cost. However, characteristics of strains for whole-cell biocatalysis and mechanism of such process are unclear. We compared three different Saccharomyces cerevisiae strains (liquor, wine, and baker's yeasts) in terms of concentration variations of substrate (raffinose), target product (melibiose), and by-products (fructose and galactose) in whole-cell biocatalysis process. Distinct difference was observed in whole-cell catalytic efficiency among three strains. Furthermore, activities of key enzymes (invertase, α-galactosidase, and fructose transporter) involved in process and expression levels of their coding genes (suc2, mel1, and fsy1) were investigated. Conservation of key genes in S. cerevisiae strains was also evaluated. Results show that whole-cell catalytic efficiency of S. cerevisiae in the raffinose substrate was closely related to activity of key enzymes and expression of their coding genes. Finally, we summarized characteristics of producing strain that offered advantages, as well as contributions of key genes to excellent strains. Furthermore, we presented a dynamic mechanism model to achieve some mechanism insight for this whole-cell biocatalytic process. This pioneering study should contribute to improvement of whole-cell biocatalytic production of melibiose from raffinose.

  15. Infrared matrix isolation and theoretical studies of reactions of ozone with bicyclic alkenes: α-pinene, norbornene, and norbornadiene.

    PubMed

    Kugel, Roger W; Ault, Bruce S

    2015-01-15

    The reactions of ozone with three bicyclic alkenes, α-pinene, norbornene, and norbornadiene, were studied by low-temperature (14 K), argon matrix isolation infrared spectroscopy including (18)O isotope-labeling studies. Theoretical calculations of some of the proposed reaction intermediates and products were carried out using the Gaussian 09 suite of programs, applying density functional theory (DFT), the B3LYP functional, and the 6-311G++(d,2p) basis set. In the α-pinene/ozone system, the thermal reaction between α-pinene and ozone was too slow to observe under the twin-jet or merged-jet deposition conditions of these experiments. However, red light (λ ≥ 600 nm) irradiation of the argon matrixes containing α-pinene and ozone caused new infrared peaks to appear that could be readily assigned to reaction products of α-pinene with O((3)P) resulting from ozone photolysis: α-pinene oxide (with an epoxide ring) and two isomeric ketones. Norbornene and norbornadiene were both found to react with ozone in the gas phase during twin-jet or merged-jet deposition of these mixtures with argon. New peaks observed in the infrared spectra were assigned to the primary ozonides, Criegee intermediates, and secondary ozonides of norbornene and norbornadiene, indicating that the bulk of these reactions proceeded via the "classic" Criegee mechanism for ozonolysis of alkenes. Calculated infrared frequencies and molecular energies support these conclusions. Ultraviolet irradiation of these mixtures resulted in complete decomposition of the early intermediates and the formation of acids, aldehydes, alcohols, carbon dioxide, and carbon monoxide. In any case, no evidence for "unusual" chemistry, prompted by the bicyclic nature of the reactants, was observed.

  16. Markedly improving asymmetric oxidation of 1-(4-methoxyphenyl) ethanol with Acetobacter sp. CCTCC M209061 cells by adding deep eutectic solvent in a two-phase system.

    PubMed

    Wei, Ping; Liang, Jing; Cheng, Jing; Zong, Min-Hua; Lou, Wen-Yong

    2016-01-13

    Enantiopure (S)-1-(4-methoxyphenyl) ethanol {(S)-MOPE} can be employed as an important synthon for the synthesis of cycloalkyl [b] indoles with the treatment function for general allergic response. To date, the biocatalytic resolution of racemic MOPE through asymmetric oxidation in the biphasic system has remained largely unexplored. Additionally, deep eutectic solvents (DESs), as a new class of promising green solvents, have recently gained increasing attention in biocatalysis for their excellent properties and many successful examples in biocatalytic processes. In this study, the biocatalytic asymmetric oxidation of MOPE to get (S)-MOPE using Acetobacter sp. CCTCC M209061 cells was investigated in different two-phase systems, and adding DES in a biphasic system was also explored to further improve the reaction efficiency of the biocatalytic oxidation. Of all the examined water-immiscible organic solvents and ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophoshpate ([C4MIM][PF6]) afforded the best results, and consequently was selected as the second phase of a two-phase system for the asymmetric oxidation of MOPE with immobilized Acetobacter sp. CCTCC M209061 cells. For the reaction performed in the [C4MIM][PF6]/buffer biphasic system, under the optimized conditions, the initial reaction rate, the maximum conversion and the residual substrate e.e. recorded 97.8 μmol/min, 50.5 and >99.9 % after 10 h reaction. Furthermore, adding the DES [ChCl][Gly] (10 %, v/v) to the aqueous phase, the efficiency of the biocatalytic oxidation was rose markedly. The optimal substrate concentration and the initial reaction rate were significantly increased to 80 mmol/L and 124.0 μmol/min, respectively, and the reaction time was shortened to 7 h with 51.3 % conversion. The immobilized cell still retained over 72 % of its initial activity after 9 batches of successive reuse in the [C4MIM][PF6]/[ChCl][Gly]-containing buffer system. Additionally, the efficient biocatalytic

  17. Determination of alkenes in cracking products by normal-phase high-performance liquid chromatography-diode array detection.

    PubMed

    Tomić, Tatjana; Babić, Sandra; Nasipak, Nada Uzorinac; Ruszkowski, Maja Fabulić; Skrobonja, Livijana; Kastelan-Macan, Marija

    2009-05-01

    Alkene content determinations in fluid catalytic cracking (FCC) liquid products were performed by means of normal-phase high-performance liquid chromatography (NP-HPLC) with diode array detection (UV/DAD). Separation of alkenes from aromatic hydrocarbons was performed on amino-modified silica gel column with n-heptane as mobile phase. The column has a little affinity to alkenes and saturated hydrocarbons and a pronounced affinity to aromatic compounds. The problem of alkenes and saturates co-elution on this column type was overcome with the detection system, UV/DAD, sensitive and selective to alkenes, while saturates are inactive in UV field. Total alkene content was determined as a sum of mono- and dialkene groups quantified by external standard method. Validation and verification of the developed method proved their applicability. The following criteria were used to validate the HPLC-DAD method: selectivity, linearity, precision, limits of detection and quantification. Alkene contents were quantified with the external standard method of wide calibration range, so both low and high alkene contents can be determined by the single calibration. Correlation coefficients were higher than 0.99. Precision was evaluated as repeatability and intermediary precision with relative standard deviations less than 5%. Some structural investigation of alkene groups was performed to confirm the assumption. Proposed method was compared with certified NMR method. Six commercial motor gasoline samples were analyzed by these two methods. Obtained results indicate good agreement between alkene content determined by both methods. The developed method was applied to the determination of alkene content in liquid FCC products in the boiling range from 70 degrees C to 190 degrees C.

  18. Hypervalent iodine(III)-mediated cyclopropa(e)nation of alkenes/alkynes under mild conditions.

    PubMed

    Lin, Shaoxia; Li, Mengru; Dong, Zhiyong; Liang, Fushun; Zhang, Jingping

    2014-02-28

    Hypervalent iodine(III)-mediated dioxygenation and diamination of alkenes have been previously developed. In this study, the potential application of hypervalent iodine(III) reagent was successfully extended to the dialkylation and cyclopropa(e)nation of unsaturated alkenes and alkynes. The reactions of alkenes with malononitrile and other active methylene compounds as the carbon nucleophiles give access to multisubstituted cyclopropane derivatives in moderate to excellent yields. Both electron-rich and electron-deficient alkenes are suitable substrates. Alkynes, no matter terminal or internal alkynes, work well, affording the corresponding highly functionalized cyclopropenes efficiently. A plausible mechanism of iodo(III)cyclopropanation, ring opening attack by the carbon-nucleophile, and recyclization was proposed for the cyclopropanation of trans-alkene substrates. The cyclopropenation was thought to proceed via iodo(III)cyclopropanation, ring-opening attack by the carbon-nucleophile, recyclization into a four-membered iodo(III)cyclobutene and final reductive elimination. The protocol might provide a complementary route to cyclopropanation/cyclopropenation.

  19. Adsorption of alkenes on acidic zeolites. Theoretical study based on the electron charge density.

    PubMed

    Zalazar, M Fernanda; Duarte, Darío J R; Peruchena, Nélida M

    2009-12-10

    In the present work, experiments on electron density changes in the adsorption process of alkenes on acidic zeolites, in the framework of atoms in molecules theory (AIM), were carried out. Electron densities were obtained at MP2 and B3LYP levels using a 6-31++G(d,p) basis set. This study explores the energetic and the electron density redistributions associated with O-H...pi interactions. The main purpose of this work is to provide an answer to the following questions: (a) Which and how large are the changes induced on the molecular electron distribution by the formation of adsorbed alkenes? (b) Can a reasonable estimate of the adsorption energy of alkenes on the active site of zeolite be solely calculated from an analysis of the electron densities? We have used topological parameters to determine the strength and nature of the interactions in the active site of the zeolite. All the results derived from the electron density analysis show that the stabilization of the adsorbed alkenes follows the order isobutene > trans-2-butene congruent with 1-butene congruent with propene > ethene, reflecting the order of basicity of C=C bonds, i.e., (C(ter)=C(prim)) > (C(sec)=C(sec)) congruent with (C(prim)=C(sec)) > (C(prim)=C(prim)). In addition, we have found a useful set of topological parameters that are good for estimating the adsorption energy in adsorbed alkenes.

  20. Stability of bound species during alkene reactions on solid acids

    NASA Astrophysics Data System (ADS)

    Sarazen, Michele L.; Iglesia, Enrique

    2017-05-01

    This study reports the thermodynamics of bound species derived from ethene, propene, n-butene, and isobutene on solid acids with diverse strength and confining voids. Density functional theory (DFT) and kinetic data indicate that covalently bound alkoxides form C-C bonds in the kinetically relevant step for dimerization turnovers on protons within TON (0.57 nm) and MOR (0.67 nm) zeolitic channels and on stronger acids HPW (polyoxometalate clusters on silica). Turnover rates for mixed alkenes give relative alkoxide stabilities; the respective adsorption constants are obtained from in situ infrared spectra. Tertiary alkoxides (from isobutene) within larger voids (MOR, HPW) are more stable than less substituted isomers but are destabilized within smaller concave environments (TON) because framework distortions are required to avoid steric repulsion. Adsorption constants are similar on MOR and HPW for each alkoxide, indicating that binding is insensitive to acid strength for covalently bound species. DFT-derived formation free energies for alkoxides with different framework attachments and backbone length/structure agree with measurements when dispersion forces, which mediate stabilization by confinement in host-guest systems, are considered. Theory reveals previously unrecognized framework distortions that balance the C-O bond lengths required for covalency with host-guest distances that maximize van der Waals contacts. These distortions, reported here as changes in O-atom locations and dihedral angles, become stronger for larger, more substituted alkoxides. The thermodynamic properties reported here for alkoxides and acid hosts differing in size and conjugate-anion stability are benchmarked against DFT-derived free energies; their details are essential to design host-guest pairs that direct alkoxide species toward specific products.

  1. Stability of bound species during alkene reactions on solid acids.

    PubMed

    Sarazen, Michele L; Iglesia, Enrique

    2017-05-16

    This study reports the thermodynamics of bound species derived from ethene, propene, n-butene, and isobutene on solid acids with diverse strength and confining voids. Density functional theory (DFT) and kinetic data indicate that covalently bound alkoxides form C-C bonds in the kinetically relevant step for dimerization turnovers on protons within TON (0.57 nm) and MOR (0.67 nm) zeolitic channels and on stronger acids HPW (polyoxometalate clusters on silica). Turnover rates for mixed alkenes give relative alkoxide stabilities; the respective adsorption constants are obtained from in situ infrared spectra. Tertiary alkoxides (from isobutene) within larger voids (MOR, HPW) are more stable than less substituted isomers but are destabilized within smaller concave environments (TON) because framework distortions are required to avoid steric repulsion. Adsorption constants are similar on MOR and HPW for each alkoxide, indicating that binding is insensitive to acid strength for covalently bound species. DFT-derived formation free energies for alkoxides with different framework attachments and backbone length/structure agree with measurements when dispersion forces, which mediate stabilization by confinement in host-guest systems, are considered. Theory reveals previously unrecognized framework distortions that balance the C-O bond lengths required for covalency with host-guest distances that maximize van der Waals contacts. These distortions, reported here as changes in O-atom locations and dihedral angles, become stronger for larger, more substituted alkoxides. The thermodynamic properties reported here for alkoxides and acid hosts differing in size and conjugate-anion stability are benchmarked against DFT-derived free energies; their details are essential to design host-guest pairs that direct alkoxide species toward specific products.

  2. Effects of chemical complexity on the autoxidation mechanisms of endocyclic alkene ozonolysis products: from methylcyclohexenes toward understanding α-pinene.

    PubMed

    Rissanen, Matti P; Kurtén, Theo; Sipilä, Mikko; Thornton, Joel A; Kausiala, Oskari; Garmash, Olga; Kjaergaard, Henrik G; Petäjä, Tuukka; Worsnop, Douglas R; Ehn, Mikael; Kulmala, Markku

    2015-05-14

    Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4-methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3(-)) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

  3. Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene

    SciTech Connect

    Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko; Thornton, Joel A.; Kausiala, Oskari; Garmash, Olga; Kjaergaard, Henrik G.; Petäjä, Tuukka; Worsnop, Douglas R.; Ehn, Mikael; Kulmala, Markku

    2015-05-14

    Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4- methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3 −) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with an autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.

  4. Effects of Chemical Complexity on the Autoxidation Mechanisms of Endocyclic Alkene Ozonolysis Products: From Methylcyclohexenes toward Understanding α-Pinene

    DOE PAGES

    Rissanen, Matti P.; Kurtén, Theo; Sipilä, Mikko; ...

    2015-05-14

    Formation of highly oxidized, multifunctional products in the ozonolysis of three endocyclic alkenes, 1- methylcyclohexene, 4- methylcyclohexene, and α-pinene, was investigated using a chemical ionization atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometer with a nitrate ion (NO3 −) based ionization scheme. The experiments were performed in borosilicate glass flow tube reactors at room temperature (T = 293 ± 3 K) and at ambient pressure. An ensemble of oxidized monomer and dimer products was detected, with elemental compositions obtained from the high-resolution mass spectra. The monomer product distributions have O/C ratios from 0.8 to 1.6 and can be explained with anmore » autocatalytic oxidation mechanism (=autoxidation) where the oxygen-centered peroxy radical (RO2) intermediates internally rearrange by intramolecular hydrogen shift reactions, enabling more oxygen molecules to attach to the carbon backbone. Dimer distributions are proposed to form by homogeneous peroxy radical recombination and cross combination reactions. These conclusions were supported by experiments where H atoms were exchanged to D atoms by addition of D2O to the carrier gas flow. Methylcyclohexenes were observed to autoxidize in accordance with our previous work on cyclohexene, whereas in α-pinene ozonolysis different mechanistic steps are needed to explain the products observed.« less

  5. Inhibitory potency of 4-carbon alkanes and alkenes toward CYP2E1 activity.

    PubMed

    Hartman, Jessica H; Miller, Grover P; Boysen, Gunnar

    2014-04-06

    CYP2E1 has been implicated in the bioactivation of many small molecules into reactive metabolites which form adducts with proteins and DNA, and thus a better understanding of the molecular determinants of its selectivity are critical for accurate toxicological predictions. In this study, we determined the potency of inhibition of human CYP2E1 for various 4-carbon alkanes, alkenes and alcohols. In addition, known CYP2E1 substrates and inhibitors including 4-methylpyrazole, aniline, and dimethylnitrosamine were included to determine their relative potencies. Of the 1,3-butadiene-derived metabolites studied, 3,4-epoxy-1-butene was the strongest inhibitor with an IC50 of 110 μM compared to 1700 μM and 6600 μM for 1,2-butenediol and 1,2:3,4-diepoxybutane, respectively. Compared to known inhibitors, inhibitory potency of 3,4-epoxy-1-butene is between 4-methylpyrazole (IC50 = 1.8 μM) and dimethylnitrosamine (IC50 = 230 μM). All three butadiene metabolites inhibit CYP2E1 activity through a simple competitive mechanism. Among the 4-carbon compounds studied, the presence and location of polar groups seems to influence inhibitory potency. To further examine this notion, the investigation was extended to include structurally and chemically similar analogues, including propylene oxide and various butane alcohols. Those results demonstrated preferential recognition of CYP2E1 toward the type and location of polar and hydrophobic structural elements. Taken together, CYP2E1 metabolism may be modified in vivo by exposure to 4-carbon compounds, such as drugs, and nutritional constituents, a finding that highlights the complexity of exposure to mixtures.

  6. Palladium-catalyzed synthesis of 2,1'-disubstituted tetrahydrofurans from gamma-hydroxy internal alkenes. Evidence for alkene insertion into a Pd-O bond and stereochemical scrambling via beta-hydride elimination.

    PubMed

    Hay, Michael B; Wolfe, John P

    2005-11-30

    Palladium-catalyzed reactions of gamma-hydroxy internal acyclic alkenes with aryl bromides afford 2,1'-disubstituted tetrahydrofurans in good yields with diastereoselectivities of 3-5:1. The analogous transformations of substrates bearing internal cyclic alkenes afford fused bicyclic and spirocyclic tetrahydrofuran derivatives in good yields with excellent diastereoselectivities (>20:1). A series of deuterium labeling experiments indicate that the origin of the modest diastereoselectivity in reactions of acyclic internal alkene substrates likely derives from a series of reversible beta-hydride elimination and sigma-bond rotation processes that occur following a rare intramolecular alkene syn-insertion into an intermediate Pd(Ar)(OR) complex. In addition, these studies shed light on the chemoselectivity of insertion, suggesting that the alkene inserts into the Pd-O bond in preference to the Pd-C bond.

  7. Palladium-Catalyzed Synthesis of 2,1′-Disubstituted Tetrahydrofurans from γ-Hydroxy Internal Alkenes. Evidence for Alkene Insertion into a Pd-O bond and Stereochemical Scrambling via β-Hydride Elimination

    PubMed Central

    Hay, Michael B.; Wolfe, John P.

    2009-01-01

    Palladium-catalyzed reactions of γ-hydroxy internal acyclic alkenes with aryl bromides afford 2,1′-disubstituted tetrahydrofurans in good yields with diastereoselectivities of 3-5:1. The analogous transformations of substrates bearing internal cyclic alkenes afford fused bicyclic and spirocyclic tetrahydrofuran derivatives in good yields with excellent diastereoselectivities (>20:1). A series of deuterium labeling experiments indicate that the origin of the modest diastereoselectivity in reactions of acyclic internal alkene substrates likely derives from a series of reversible β-hydride elimination and σ-bond rotation processes that occur following a rare intramolecular syn-alkene insertion into an intermediate Pd(Ar)(OR) complex. In addition, these studies shed light on the chemoselectivity of insertion, suggesting that the alkene inserts into the Pd-O bond in preference to the Pd-C bond. PMID:16305233

  8. DualPhos: a versatile, chemoselective reagent for two-carbon aldehyde to latent (E)-alkenal homologation and application in the total synthesis of phomolide G

    PubMed Central

    McLeod, David

    2016-01-01

    Advances on the use of the 2-pinacolacetal-tripropylphosphonium salt DualPhos as a general reagent for the two-carbon aldehyde to alkenal homologation and a chemoselective iron (III) chloride mediated deprotection are described. The strategy allows isolation of the latent alkenal intermediates or direct hydrolysis to (E)-alkenals. The robust chemical stability of the latent alkenals is demonstrated in a total synthesis of the macrolactone phomolide G. PMID:28018615

  9. Metal-Free C–H Alkyliminylation and Acylation of Alkenes with Secondary Amides

    NASA Astrophysics Data System (ADS)

    Huang, Pei-Qiang; Huang, Ying-Hong; Geng, Hui; Ye, Jian-Liang

    2016-06-01

    Carbon–carbon bond formation by metal-free cross-coupling of two reactants with low reactivity represents a challenge in organic synthesis. Secondary amides and alkenes are two classes of bench-stable compounds. The low electrophilicity of the former and low nucleophilicity of the latter make the direct coupling of these two partners challenging yet highly desirable. We report herein an unprecedented intermolecular reaction of secondary amides with alkenes to afford α,β-unsaturated ketimines or enones, which are versatile intermediates for organic synthesis and are prevalent in bioactive compounds and functional materials. Our strategy relies on the chemoselective activation of the secondary amide with trifluoromethanesulfonic anhydride (Tf2O)/2-fluoropyridine to generate a highly reactive nitrilium intermediate, which reacts efficiently with alkenes. This metal-free synthesis is characterized by its mild reaction conditions, excellent functional group tolerance and chemoselectivity, allowing the preparation of multi-functionalized compounds without using protecting groups.

  10. Stereoselective synthesis of imidazolidin-2-ones via Pd-catalyzed alkene carboamination. Scope and limitations

    PubMed Central

    Fritz, Jonathan A.; Wolfe, John P.

    2008-01-01

    A method for the synthesis of imidazolidin-2-ones from N-allylureas and aryl or alkenyl bromides via Pd-catalyzed carboamination reactions is described. The N-allylurea precursors are prepared in one step from readily available allylic amines and isocyanates, and the Pd-catalyzed reactions effect the formation of a C–C bond, a C–N bond, and up to two stereocenters in a single step. Good diastereoselectivities are obtained for the conversion of substrates bearing allylic substituents to 4,5-disubstituted imidazolidin-2-ones, and excellent selectivity for the generation of products resulting from syn-addition across the alkene is observed when substrates derived from cyclic alkenes or E-1,2-disubstituted alkenes are employed. A brief discussion of reaction mechanism and product stereochemistry is presented. PMID:19122758

  11. The Nitrilimine-Alkene Cycloaddition Regioselectivity Rationalized by Density Functional Theory Reactivity Indices.

    PubMed

    Molteni, Giorgio; Ponti, Alessandro

    2017-01-26

    Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine-alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine-alkene cycloadditions were analyzed, for which we could find regioselectivity data in the literature. We computed DFT reactivity indices at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d,p) and employed the grand potential stabilization criterion to calculate the preferred regioisomer. Experimental and calculated regioselectivity agree in the vast majority of cases. It was concluded that predominance of a single regioisomer can be obtained by maximizing (i) the chemical potential difference between nitrilimine and alkene and (ii) the local softness difference between the reactive atomic sites within each reactant. Such maximization can be achieved by carefully selecting the substituents on both reactants.

  12. ORGANIC CHEMISTRY. Iron-catalyzed intermolecular [2+2] cycloadditions of unactivated alkenes.

    PubMed

    Hoyt, Jordan M; Schmidt, Valerie A; Tondreau, Aaron M; Chirik, Paul J

    2015-08-28

    Cycloadditions, such as the [4+2] Diels-Alder reaction to form six-membered rings, are among the most powerful and widely used methods in synthetic chemistry. The analogous [2+2] alkene cycloaddition to synthesize cyclobutanes is kinetically accessible by photochemical methods, but the substrate scope and functional group tolerance are limited. Here, we report iron-catalyzed intermolecular [2+2] cycloaddition of unactivated alkenes and cross cycloaddition of alkenes and dienes as regio- and stereoselective routes to cyclobutanes. Through rational ligand design, development of this base metal-catalyzed method expands the chemical space accessible from abundant hydrocarbon feedstocks. Copyright © 2015, American Association for the Advancement of Science.

  13. Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes.

    PubMed

    Tomita, Ren; Koike, Takashi; Akita, Munetaka

    2015-10-26

    A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. BCl3-mediated ene reaction of sulfur dioxide and unfunctionalized alkenes.

    PubMed

    Marković, Dean; Volla, Chandra M R; Vogel, Pierre; Varela-Alvarez, Adrián; Sordo, José A

    2010-05-25

    The first ene reactions of SO(2) and unfunctionalized alkenes are reported. Calculations suggest that the endergonic ene reactions of SO(2) with alkenes can be used to generate beta,gamma-unsaturated sulfinyl and sulfonyl compounds. Indeed, in the presence of one equivalent of BCl(3), the unstable sulfinic acid form stable sulfinic acid.BCl(3) complexes that can be reacted in situ with NCS to generate corresponding sulfonyl chlorides, or with a base to generate corresponding sulfinates. The latter can be reacted with electrophiles to generate sulfones, or with silyl chloride to form beta,gamma-unsaturated silyl sulfinates. The sulfinic acid.BCl(3) complexes can be reacted with ethers that act as oxygen nucleophiles to produce corresponding sulfinic esters. Thus one-pot, three-component synthesis of beta,gamma-unsaturated sulfonamides, sulfinyl esters and sulfones have been developed starting from alkenes and sulfur dioxide (reagent and solvent).

  15. Metal-Free C–H Alkyliminylation and Acylation of Alkenes with Secondary Amides

    PubMed Central

    Huang, Pei-Qiang; Huang, Ying-Hong; Geng, Hui; Ye, Jian-Liang

    2016-01-01

    Carbon–carbon bond formation by metal-free cross-coupling of two reactants with low reactivity represents a challenge in organic synthesis. Secondary amides and alkenes are two classes of bench-stable compounds. The low electrophilicity of the former and low nucleophilicity of the latter make the direct coupling of these two partners challenging yet highly desirable. We report herein an unprecedented intermolecular reaction of secondary amides with alkenes to afford α,β-unsaturated ketimines or enones, which are versatile intermediates for organic synthesis and are prevalent in bioactive compounds and functional materials. Our strategy relies on the chemoselective activation of the secondary amide with trifluoromethanesulfonic anhydride (Tf2O)/2-fluoropyridine to generate a highly reactive nitrilium intermediate, which reacts efficiently with alkenes. This metal-free synthesis is characterized by its mild reaction conditions, excellent functional group tolerance and chemoselectivity, allowing the preparation of multi-functionalized compounds without using protecting groups. PMID:27356173

  16. Peroxide promoted tunable decarboxylative alkylation of cinnamic acids to form alkenes or ketones under metal-free conditions.

    PubMed

    Ji, Jing; Liu, Ping; Sun, Peipei

    2015-05-01

    A tunable decarboxylative alkylation of cinnamic acids with alkanes was developed to form alkenes or ketones under transition metal-free conditions. In the presence of DTBP or DTBP/TBHP, the reaction gave alkenes and ketones respectively via a radical mechanism in moderate to good yields.

  17. Photochemical Synthesis and Ligand Exchange Reactions of Ru(CO)[subscript 4] (Eta[superscript 2]-Alkene) Compounds

    ERIC Educational Resources Information Center

    Cooke, Jason; Berry, David E.; Fawkes, Kelli L.

    2007-01-01

    The photochemical synthesis and subsequent ligand exchange reactions of Ru(CO)[subscript 4] (eta[superscript2]-alkene) compounds has provided a novel experiment for upper-level inorganic chemistry laboratory courses. The experiment is designed to provide a system in which the changing electronic properties of the alkene ligands could be easily…

  18. Highly enantioselective and anti-diastereoselective catalytic intermolecular glyoxylate-ene reactions: effect of the geometrical isomers of alkenes.

    PubMed

    Zhang, Xiang; Wang, Min; Ding, Ran; Xu, Yun-He; Loh, Teck-Peng

    2015-06-05

    An efficient method for the synthesis of homoallylic alcohols with high enantioselectivities and anti-diastereoselectivities via an In(III)-catalyzed intermolecular glyoxylate-ene reaction has been developed. The geometrical isomers of alkenes were shown to have different reactivities. Only the isomers of the alkenes having a proton β-cis to the substituent reacted in this catalytic system.

  19. Photochemical Synthesis and Ligand Exchange Reactions of Ru(CO)[subscript 4] (Eta[superscript 2]-Alkene) Compounds

    ERIC Educational Resources Information Center

    Cooke, Jason; Berry, David E.; Fawkes, Kelli L.

    2007-01-01

    The photochemical synthesis and subsequent ligand exchange reactions of Ru(CO)[subscript 4] (eta[superscript2]-alkene) compounds has provided a novel experiment for upper-level inorganic chemistry laboratory courses. The experiment is designed to provide a system in which the changing electronic properties of the alkene ligands could be easily…

  20. Mechanism of stereoselective epoxidation of alkenes by oxo-iron porphyrins

    SciTech Connect

    Joergensen, K.A.

    1987-02-04

    The structure of oxo-iron porphyrins and their stereoselective epoxidation properties of alkenes are analyzed from a theoretical point of view. It is found that the most stable structure of oxo-iron porphyrin is one in which oxygen is inserted into the iron-nitrogen bond. This structure is equivalent to some of the carbene analogues, and the bond lengths for Fe-O (1.9 A) and N-O (1.4 A) are in good agreement with those found in the nickel analogue of 6. The insertion of oxygen into the iron-nitrogen bond makes some of the d orbitals on iron available for interaction with the alkene; this type of complex is supported by recent experimental observations. The alkene can be coordinated in a perpendicular or parallel orientation at the iron atom (relative to the iron-oxygen bond), and the perpendicular orientation is found to be the most favorable. This binding of the alkene can then cause the stereoselective epoxidation properties, as the trans substituents will interact repulsively with the iron-porphyrin moiety. It is then suggested that the next step in the reaction mechanism is a slipping motion of the alkene toward the oxygen. This motion is controlled by a favorable interaction between the ..pi..* orbital of the alkene and the lone pair on the oxygen which is antisymmetric with respect to the iron-oxygen-nitrogen plane. Aspects of this type of mechanism in relation to the experimental results as well as other transition metal catalyzed epoxidation reactions are discussed.

  1. Photochemical grafting of n-alkenes onto carbon surfaces: the role of photoelectron ejection.

    PubMed

    Colavita, Paula E; Sun, Bin; Tse, Kiu-Yuen; Hamers, Robert J

    2007-11-07

    The grafting of molecular layers to carbon-based materials provides a way to combine the high chemical and thermal stability of these materials with surface properties such as chemical recognition or reactivity. The functionalization of surfaces with ultraviolet light has emerged as a way to modify difficult-to-functionalize materials, such as diamond. We have performed a combined experimental and computational investigation of the photochemical reaction of terminal alkenes with hydrogen-terminated carbon surfaces. 1-Alkenes carrying various terminal functional groups (-NHCOCF3, -NHCOO(tert-butyl), -COOCH3, -CH3) were grafted from the neat liquids using 254 nm light. These layers were characterized using X-ray Photoelectron Spectroscopy and Infrared Reflectance Absorption Spectroscopy. Pronounced differences in reactivity were observed between the molecules: trifluoroacetamide-terminated alkenes grafted the fastest and yielded self-terminating layers after approximately 4 h. Ultraviolet photoelectron spectroscopy and photocurrent measurements show that the grafting reaction involves photoemission of electrons into the liquid. Density functional calculations show that the reactivities of the four molecules are correlated with their electron affinities, with the trifluoroacetamide group acting as the best electron acceptor and having the highest reactivity. Our results demonstrate that photoejection of electrons from the solid into the acceptor levels of the alkenes initiates the functionalization reaction and controls the overall rate. Finally, marginally reactive n-alkenes were induced to react and form dense monolayers by seeding the carbon surface with small amounts of a good electron acceptor, such as the trifluoroacetamide moiety. This study provides important new mechanistic insights into the use of ultraviolet light to initiate grafting of alkenes onto surfaces.

  2. Cellulose Digestion and Metabolism Induced Biocatalytic Transitions in Anaerobic Microbial Ecosystems

    PubMed Central

    Yamazawa, Akira; Iikura, Tomohiro; Morioka, Yusuke; Shino, Amiu; Ogata, Yoshiyuki; Date, Yasuhiro; Kikuchi, Jun

    2013-01-01

    Anaerobic digestion of highly polymerized biomass by microbial communities present in diverse microbial ecosystems is an indispensable metabolic process for biogeochemical cycling in nature and for industrial activities required to maintain a sustainable society. Therefore, the evaluation of the complicated microbial metabolomics presents a significant challenge. We here describe a comprehensive strategy for characterizing the degradation of highly crystallized bacterial cellulose (BC) that is accompanied by metabolite production for identifying the responsible biocatalysts, including microorganisms and their metabolic functions. To this end, we employed two-dimensional solid- and one-dimensional solution-state nuclear magnetic resonance (NMR) profiling combined with a metagenomic approach using stable isotope labeling. The key components of biocatalytic reactions determined using a metagenomic approach were correlated with cellulose degradation and metabolic products. The results indicate that BC degradation was mediated by cellulases that contain carbohydrate-binding modules and that belong to structural type A. The degradation reactions induced the metabolic dynamics of the microbial community and produced organic compounds, such as acetic acid and propionic acid, mainly metabolized by clostridial species. This combinatorial, functional and structural metagenomic approach is useful for the comprehensive characterization of biomass degradation, metabolic dynamics and their key components in diverse ecosystems. PMID:24958386

  3. Building Bridges: Biocatalytic C–C-Bond Formation toward Multifunctional Products

    PubMed Central

    2016-01-01

    Carbon–carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C–C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C–C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C–C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand. PMID:27398261

  4. Derivatization of single-walled carbon nanotubes with redox mediator for biocatalytic oxygen electrodes.

    PubMed

    Sadowska, K; Stolarczyk, K; Biernat, J F; Roberts, K P; Rogalski, J; Bilewicz, R

    2010-11-01

    Single-walled carbon nanotubes (SWCNTs) were covalently modified with a redox mediator derived from 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS), and implemented in the construction of electrodes for biocatalytic oxygen reduction. The procedure is based on: covalent bonding of mediator to nanotubes, placing the nanotubes directly on the carbon electrode surface and covering the nanostructured electrode with a Nafion film containing laccase as the biocatalyst. The modified electrode is stable and the problem of mediator (ABTS) leaking from the film is eliminated by binding it covalently to the nanotubes. Three different synthetic approaches were used to obtain ABTS-modified carbon nanotubes. Nanotubes were modified at ends/defect sites or on the nanotube sidewalls and characterized by Raman spectroscopy, TGA and electrochemistry. The accessibility of differently located ABTS units by the laccase active center and mediation of electron transfer were studied by cyclic voltammetry. The surface concentrations of ABTS groups electrically connected with the electrode were compared for each of the electrodes based on the charges of the voltammetric peaks recorded in the deaerated solution. The nanotube modification procedure giving the best parameters of the catalytic process was selected.

  5. Building Bridges: Biocatalytic C-C-Bond Formation toward Multifunctional Products.

    PubMed

    Schmidt, Nina G; Eger, Elisabeth; Kroutil, Wolfgang

    2016-07-01

    Carbon-carbon bond formation is the key reaction for organic synthesis to construct the carbon framework of organic molecules. The review gives a selection of biocatalytic C-C-bond-forming reactions which have been investigated during the last 5 years and which have already been proven to be applicable for organic synthesis. In most cases, the reactions lead to products functionalized at the site of C-C-bond formation (e.g., α-hydroxy ketones, aminoalcohols, diols, 1,4-diketones, etc.) or allow to decorate aromatic and heteroaromatic molecules. Furthermore, examples for cyclization of (non)natural precursors leading to saturated carbocycles are given as well as the stereoselective cyclopropanation of olefins affording cyclopropanes. Although many tools are already available, recent research also makes it clear that nature provides an even broader set of enzymes to perform specific C-C coupling reactions. The possibilities are without limit; however, a big library of variants for different types of reactions is required to have the specific enzyme for a desired specific (stereoselective) reaction at hand.

  6. Biocatalytic Synthesis of Flavonoid Esters by Lipases and Their Biological Benefits.

    PubMed

    de Araújo, Maria Elisa M B; Franco, Yollanda E M; Messias, Marcia C F; Longato, Giovanna B; Pamphile, João A; Carvalho, Patricia de O

    2017-01-01

    Several studies have described important biological activities of flavonoids such as coronary heart disease prevention, hepatoprotective, anti-inflammatory and anticancer activities, enzyme inhibition activity, and antibacterial, antifungal, and antiviral activities. Flavonoids show promising activity as natural plant-based antioxidants due to their antioxidant and free radical scavenging properties. However, their primary applications as antioxidants in the pharmaceutical, cosmetic, and food industries are limited because of their moderately hydrophilic nature. Enzymatic acylation of natural polyphenols with fatty acids or other acyl donors has been suggested for improving the lipophilic nature of the glycosylated flavonoids. This approach increases flavonoid solubility and stability in lipophilic systems. Acylation of flavonoids with different acyl donors may also introduce beneficial properties to the molecule, such as penetration through the cell membrane and improved antioxidant, antimicrobial, anti-inflammatory, antiproliferative, cytogenetic, and enzyme inhibition activities. Chemical methods for the synthesis of flavonoid esters lead to the formation of side products and the simultaneous decomposition of the flavonoids due to harsh reaction conditions. In contrast, biocatalytic acylation of flavonoids by lipases offers advantages associated to the wide availability of these enzymes, their low cost, chemo-, regio-, and enantioselectivity, mild condition processing and non-requirement of cofactors. This article is focused on the recent development of lipase-catalyzed synthesis of flavonoid esters and the impact of the acylation reaction on their biological activities. Georg Thieme Verlag KG Stuttgart · New York.

  7. Cellulose digestion and metabolism induced biocatalytic transitions in anaerobic microbial ecosystems.

    PubMed

    Yamazawa, Akira; Iikura, Tomohiro; Morioka, Yusuke; Shino, Amiu; Ogata, Yoshiyuki; Date, Yasuhiro; Kikuchi, Jun

    2013-12-31

    Anaerobic digestion of highly polymerized biomass by microbial communities present in diverse microbial ecosystems is an indispensable metabolic process for biogeochemical cycling in nature and for industrial activities required to maintain a sustainable society. Therefore, the evaluation of the complicated microbial metabolomics presents a significant challenge. We here describe a comprehensive strategy for characterizing the degradation of highly crystallized bacterial cellulose (BC) that is accompanied by metabolite production for identifying the responsible biocatalysts, including microorganisms and their metabolic functions. To this end, we employed two-dimensional solid- and one-dimensional solution-state nuclear magnetic resonance (NMR) profiling combined with a metagenomic approach using stable isotope labeling. The key components of biocatalytic reactions determined using a metagenomic approach were correlated with cellulose degradation and metabolic products. The results indicate that BC degradation was mediated by cellulases that contain carbohydrate-binding modules and that belong to structural type A. The degradation reactions induced the metabolic dynamics of the microbial community and produced organic compounds, such as acetic acid and propionic acid, mainly metabolized by clostridial species. This combinatorial, functional and structural metagenomic approach is useful for the comprehensive characterization of biomass degradation, metabolic dynamics and their key components in diverse ecosystems.

  8. Expedient synthesis of C-aryl carbohydrates by consecutive biocatalytic benzoin and aldol reactions.

    PubMed

    Hernández, Karel; Parella, Teodor; Joglar, Jesús; Bujons, Jordi; Pohl, Martina; Clapés, Pere

    2015-02-16

    The introduction of aromatic residues connected by a C-C bond into the non-reducing end of carbohydrates is highly significant for the development of innovative structures with improved binding affinity and selectivity (e.g., C-aril-sLex). In this work, an expedient asymmetric "de novo" synthetic route to new aryl carbohydrate derivatives based on two sequential stereoselectively biocatalytic carboligation reactions is presented. First, the benzoin reaction of aromatic aldehydes to dimethoxyacetaldehyde is conducted, catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I. Then, the α-hydroxyketones formed are reduced by using NaBH4 yielding the anti diol. After acetal hydrolysis, the aldol addition of dihydroxyacetone, hydroxyacetone, or glycolaldehyde catalyzed by the stereocomplementary D-fructose-6-phosphate aldolase and L-rhamnulose-1-phosphate aldolase is performed. Both aldolases accept unphosphorylated donor substrates, avoiding the need of handling the phosphate group that the dihydroxyacetone phosphate-dependent aldolases require. In this way, 6-C-aryl-L-sorbose, 6-C-aryl-L-fructose, 6-C-aryl-L-tagatose, and 5-C-aryl-L-xylose derivatives are prepared by using this methodology.

  9. Characterisation of a Recombinant Patchoulol Synthase Variant for Biocatalytic Production of Terpenes.

    PubMed

    Frister, Thore; Hartwig, Steffen; Alemdar, Semra; Schnatz, Katharina; Thöns, Laura; Scheper, Thomas; Beutel, Sascha

    2015-08-01

    The patchoulol synthase (PTS) is a multi-product sesquiterpene synthases which is the central enzyme for biosynthesis of patchouli essential oil in the patchouli plant. Sesquiterpene synthases catalyse the formation of various complex carbon backbones difficult to approach by organic synthesis. Here, we report the characterisation of a recombinant patchoulol synthase complementary DNA (cDNA) variant (PTS var. 1), exhibiting significant amino acid exchanges compared to the native PTS. The product spectrum using the natural substrate E,E-farnesyl diphosphate (FDP) as well as terpenoid products resulting from conversions employing alternative substrates was analysed by GC-MS. In respect to a potential use as a biocatalyst, important enzymatic parameters such as the optimal reaction conditions, kinetic behaviour and the product selectivity were studied as well. Adjusting the reaction conditions, an increased patchoulol ratio in the recombinant essential oil was achieved. Nevertheless, the ratio remained lower than in plant-derived patchouli oil. As alternative substrates, several prenyl diposphates were accepted and converted in numerous compounds by the PTS var. 1, revealing its great biocatalytic potential.

  10. A Biocatalytic Nanomaterial for the Label-Free Detection of Virus-Like Particles.

    PubMed

    Sykora, Sabine; Correro, M Rita; Moridi, Negar; Belliot, Gaël; Pothier, Pierre; Dudal, Yves; Corvini, Philippe F-X; Shahgaldian, Patrick

    2017-06-01

    The design of nanomaterials that are capable of specific and sensitive biomolecular recognition is an on-going challenge in the chemical and biochemical sciences. A number of sophisticated artificial systems have been designed to specifically recognize a variety of targets. However, methods based on natural biomolecular detection systems using antibodies are often superior. Besides greater affinity and selectivity, antibodies can be easily coupled to enzymatic systems that act as signal amplifiers, thus permitting impressively low detection limits. The possibility to translate this concept to artificial recognition systems remains limited due to design incompatibilities. Here we describe the synthesis of a synthetic nanomaterial capable of specific biomolecular detection by using an internal biocatalytic colorimetric detection and amplification system. The design of this nanomaterial relies on the ability to accurately grow hybrid protein-organosilica layers at the surface of silica nanoparticles. The method allows for label-free detection and quantification of targets at picomolar concentrations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

    PubMed Central

    Bogorad, Igor W.; Chen, Chang-Ting; Theisen, Matthew K.; Wu, Tung-Yun; Schlenz, Alicia R.; Lam, Albert T.; Liao, James C.

    2014-01-01

    Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C–C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through 13C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives. PMID:25355907

  12. Building carbon-carbon bonds using a biocatalytic methanol condensation cycle.

    PubMed

    Bogorad, Igor W; Chen, Chang-Ting; Theisen, Matthew K; Wu, Tung-Yun; Schlenz, Alicia R; Lam, Albert T; Liao, James C

    2014-11-11

    Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C-C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbon-conserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through (13)C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives.

  13. A continuous system for biocatalytic hydrogenation of CO2 to formate.

    PubMed

    Mourato, Cláudia; Martins, Mónica; da Silva, Sofia M; Pereira, Inês A C

    2017-03-20

    In this work a novel bioprocess for hydrogenation of CO2 to formate was developed, using whole cell catalysis by a sulfate-reducing bacterium. Three Desulfovibrio species were tested (D. vulgaris Hildenborough, D. alaskensis G20, and D. desulfuricans ATCC 27774), of which D. desulfuricans showed the highest activity, producing 12mM of formate in batch, with a production rate of 0.09mMh(-1). Gene expression analysis indicated that among the three formate dehydrogenases and five hydrogenases, the cytoplasmic FdhAB and the periplasmic [FeFe] HydAB are the main enzymes expressed in D. desulfuricans in these conditions. The new bioprocess for continuous formate production by D. desulfuricans had a maximum specific formate production rate of 14mMgdcw(-1)h(-1), and more than 45mM of formate were obtained with a production rate of 0.40mMh(-1). This is the first report of a continuous process for biocatalytic formate production.

  14. Separation, Immobilization, and Biocatalytic Utilization of Proteins by a Supramolecular Membrane

    PubMed Central

    Krieg, Elisha; Albeck, Shira; Weissman, Haim; Shimoni, Eyal; Rybtchinski, Boris

    2013-01-01

    Membrane separation of biomolecules and their application in biocatalysis is becoming increasingly important for biotechnology, demanding the development of new biocompatible materials with novel properties. In the present study, an entirely noncovalent water-based material is used as a membrane for size-selective separation, immobilization, and biocatalytic utilization of proteins. The membrane shows stable performance under physiological conditions, allowing filtration of protein mixtures with a 150 kDa molecular weight cutoff (∼8 nm hydrodynamic diameter cutoff). Due to the biocompatibility of the membrane, filtered proteins stay functionally active and retained proteins can be partially recovered. Upon filtration, large enzymes become immobilized within the membrane. They exhibit stable activity when subjected to a constant flux of substrates for prolonged periods of time, which can be used to carry out heterogeneous biocatalysis. The noncovalent membrane material can be easily disassembled, purified, reassembled, and reused, showing reproducible performance after recycling. The robustness, recyclability, versatility, and biocompatibility of the supramolecular membrane may open new avenues for manipulating biological systems. PMID:23675461

  15. Biocatalytic Production of Trehalose from Maltose by Using Whole Cells of Permeabilized Recombinant Escherichia coli

    PubMed Central

    Sun, Ye; Mei, Wending; Ouyang, Jia

    2015-01-01

    Trehalose is a non-reducing disaccharide, which can protect proteins, lipid membranes, and cells from desiccation, refrigeration, dehydration, and other harsh environments. Trehalose can be produced by different pathways and trehalose synthase pathway is a convenient, practical, and low-cost pathway for the industrial production of trehalose. In this study, 3 candidate treS genes were screened from genomic databases of Pseudomonas and expressed in Escherichia coli. One of them from P. stutzeri A1501 exhibited the best transformation ability from maltose into trehalose and the least byproduct. Thus, whole cells of this recombinant E. coli were used as biocatalyst for trehalose production. In order to improve the conversion rate of maltose to trehalose, optimization of the permeabilization and biotransformation were carried out. Under optimal conditions, 92.2 g/l trehalose was produced with a high productivity of 23.1 g/(l h). No increase of glucose was detected during the whole course. The biocatalytic process developed in this study might serve as a candidate for the large scale production of trehalose. PMID:26462117

  16. Microbiome and Biocatalytic Bacteria in Monkey Cup (Nepenthes Pitcher) Digestive Fluid.

    PubMed

    Chan, Xin-Yue; Hong, Kar-Wai; Yin, Wai-Fong; Chan, Kok-Gan

    2016-01-28

    Tropical carnivorous plant, Nepenthes, locally known as "monkey cup", utilises its pitcher as a passive trap to capture insects. It then secretes enzymes into the pitcher fluid to digest the insects for nutrients acquisition. However, little is known about the microbiota and their activity in its pitcher fluid. Eighteen bacteria phyla were detected from the metagenome study in the Nepenthes pitcher fluid. Proteobacteria, Bacteroidetes and Actinobacteria are the dominant phyla in the Nepenthes pitcher fluid. We also performed culturomics approach by isolating 18 bacteria from the Nepenthes pitcher fluid. Most of the bacterial isolates possess chitinolytic, proteolytic, amylolytic, and cellulolytic and xylanolytic activities. Fifteen putative chitinase genes were identified from the whole genome analysis on the genomes of the 18 bacteria isolated from Nepenthes pitcher fluid and expressed for chitinase assay. Of these, six clones possessed chitinase activity. In conclusion, our metagenome result shows that the Nepenthes pitcher fluid contains vast bacterial diversity and the culturomic studies confirmed the presence of biocatalytic bacteria within the Nepenthes pitcher juice which may act in symbiosis for the turn over of insects trapped in the Nepenthes pitcher fluid.

  17. Microbiome and Biocatalytic Bacteria in Monkey Cup (Nepenthes Pitcher) Digestive Fluid

    PubMed Central

    Chan, Xin-Yue; Hong, Kar-Wai; Yin, Wai-Fong; Chan, Kok-Gan

    2016-01-01

    Tropical carnivorous plant, Nepenthes, locally known as “monkey cup”, utilises its pitcher as a passive trap to capture insects. It then secretes enzymes into the pitcher fluid to digest the insects for nutrients acquisition. However, little is known about the microbiota and their activity in its pitcher fluid. Eighteen bacteria phyla were detected from the metagenome study in the Nepenthes pitcher fluid. Proteobacteria, Bacteroidetes and Actinobacteria are the dominant phyla in the Nepenthes pitcher fluid. We also performed culturomics approach by isolating 18 bacteria from the Nepenthes pitcher fluid. Most of the bacterial isolates possess chitinolytic, proteolytic, amylolytic, and cellulolytic and xylanolytic activities. Fifteen putative chitinase genes were identified from the whole genome analysis on the genomes of the 18 bacteria isolated from Nepenthes pitcher fluid and expressed for chitinase assay. Of these, six clones possessed chitinase activity. In conclusion, our metagenome result shows that the Nepenthes pitcher fluid contains vast bacterial diversity and the culturomic studies confirmed the presence of biocatalytic bacteria within the Nepenthes pitcher juice which may act in symbiosis for the turn over of insects trapped in the Nepenthes pitcher fluid. PMID:26817720

  18. Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede, Chamberlinius hualienensis.

    PubMed

    Dadashipour, Mohammad; Ishida, Yuko; Yamamoto, Kazunori; Asano, Yasuhisa

    2015-08-25

    Hydroxynitrile lyase (HNL) catalyzes the degradation of cyanohydrins and causes the release of hydrogen cyanide (cyanogenesis). HNL can enantioselectively produce cyanohydrins, which are valuable building blocks for the synthesis of fine chemicals and pharmaceuticals, and is used as an important biocatalyst in industrial biotechnology. Currently, HNLs are isolated from plants and bacteria. Because industrial biotechnology requires more efficient and stable enzymes for sustainable development, we must continuously explore other potential enzyme sources for the desired HNLs. Despite the abundance of cyanogenic millipedes in the world, there has been no precise study of the HNLs from these arthropods. Here we report the isolation of HNL from the cyanide-emitting invasive millipede Chamberlinius hualienensis, along with its molecular properties and application in biocatalysis. The purified enzyme displays a very high specific activity in the synthesis of mandelonitrile. It is a glycosylated homodimer protein and shows no apparent sequence identity or homology with proteins in the known databases. It shows biocatalytic activity for the condensation of various aromatic aldehydes with potassium cyanide to produce cyanohydrins and has high stability over a wide range of temperatures and pH values. It catalyzes the synthesis of (R)-mandelonitrile from benzaldehyde with a 99% enantiomeric excess, without using any organic solvents. Arthropod fauna comprise 80% of terrestrial animals. We propose that these animals can be valuable resources for exploring not only HNLs but also diverse, efficient, and stable biocatalysts in industrial biotechnology.

  19. Antagonistic Enzymes in a Biocatalytic pH Feedback System Program Autonomous DNA Hydrogel Life Cycles.

    PubMed

    Heinen, Laura; Heuser, Thomas; Steinschulte, Alexander; Walther, Andreas

    2017-08-09

    Enzymes regulate complex functions and active behavior in natural systems and have shown increasing prospect for developing self-regulating soft matter systems. Striving for advanced autonomous hydrogel materials with fully programmable, self-regulated life cycles, we combine two enzymes with an antagonistic pH-modulating effect in a feedback-controlled biocatalytic reaction network (BRN) and couple it to pH-responsive DNA hydrogels to realize hydrogel systems with distinct preprogrammable lag times and lifetimes in closed systems. The BRN enables precise and orthogonal internal temporal control of the "ON" and "OFF" switching times of the temporary gel state by modulation of programmable, nonlinear pH changes. The time scales are tunable by variation of the enzyme concentrations and additional buffer substances. The resulting material system operates in full autonomy after injection of the chemical fuels driving the BRN. The concept may open new applications inherent to DNA hydrogels, for instance, autonomous shape memory behavior for soft robotics. We further foresee general applicability to achieve autonomous life cycles in other pH switchable systems.

  20. Biocatalytic Production of Trehalose from Maltose by Using Whole Cells of Permeabilized Recombinant Escherichia coli.

    PubMed

    Zheng, Zhaojuan; Xu, Ying; Sun, Ye; Mei, Wending; Ouyang, Jia

    2015-01-01

    Trehalose is a non-reducing disaccharide, which can protect proteins, lipid membranes, and cells from desiccation, refrigeration, dehydration, and other harsh environments. Trehalose can be produced by different pathways and trehalose synthase pathway is a convenient, practical, and low-cost pathway for the industrial production of trehalose. In this study, 3 candidate treS genes were screened from genomic databases of Pseudomonas and expressed in Escherichia coli. One of them from P. stutzeri A1501 exhibited the best transformation ability from maltose into trehalose and the least byproduct. Thus, whole cells of this recombinant E. coli were used as biocatalyst for trehalose production. In order to improve the conversion rate of maltose to trehalose, optimization of the permeabilization and biotransformation were carried out. Under optimal conditions, 92.2 g/l trehalose was produced with a high productivity of 23.1 g/(l h). No increase of glucose was detected during the whole course. The biocatalytic process developed in this study might serve as a candidate for the large scale production of trehalose.

  1. Discovery and molecular and biocatalytic properties of hydroxynitrile lyase from an invasive millipede, Chamberlinius hualienensis

    PubMed Central

    Dadashipour, Mohammad; Ishida, Yuko; Yamamoto, Kazunori; Asano, Yasuhisa

    2015-01-01

    Hydroxynitrile lyase (HNL) catalyzes the degradation of cyanohydrins and causes the release of hydrogen cyanide (cyanogenesis). HNL can enantioselectively produce cyanohydrins, which are valuable building blocks for the synthesis of fine chemicals and pharmaceuticals, and is used as an important biocatalyst in industrial biotechnology. Currently, HNLs are isolated from plants and bacteria. Because industrial biotechnology requires more efficient and stable enzymes for sustainable development, we must continuously explore other potential enzyme sources for the desired HNLs. Despite the abundance of cyanogenic millipedes in the world, there has been no precise study of the HNLs from these arthropods. Here we report the isolation of HNL from the cyanide-emitting invasive millipede Chamberlinius hualienensis, along with its molecular properties and application in biocatalysis. The purified enzyme displays a very high specific activity in the synthesis of mandelonitrile. It is a glycosylated homodimer protein and shows no apparent sequence identity or homology with proteins in the known databases. It shows biocatalytic activity for the condensation of various aromatic aldehydes with potassium cyanide to produce cyanohydrins and has high stability over a wide range of temperatures and pH values. It catalyzes the synthesis of (R)-mandelonitrile from benzaldehyde with a 99% enantiomeric excess, without using any organic solvents. Arthropod fauna comprise 80% of terrestrial animals. We propose that these animals can be valuable resources for exploring not only HNLs but also diverse, efficient, and stable biocatalysts in industrial biotechnology. PMID:26261304

  2. Cascade multicomponent synthesis of indoles, pyrazoles, and pyridazinones by functionalization of alkenes.

    PubMed

    Matcha, Kiran; Antonchick, Andrey P

    2014-10-27

    The development of multicomponent reactions for indole synthesis is demanding and has hardly been explored. The present study describes the development of a novel multicomponent, cascade approach for indole synthesis. Various substituted indole derivatives were obtained from simple reagents, such as unfunctionalized alkenes, diazonium salts, and sodium triflinate, by using an established straightforward and regioselective method. The method is based on the radical trifluoromethylation of alkenes as an entry into Fischer indole synthesis. Besides indole synthesis, the application of the multicomponent cascade reaction to the synthesis of pyrazoles and pyridazinones is described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. A new approach to ferrocene derived alkenes via copper-catalyzed olefination

    PubMed Central

    Muzalevskiy, Vasily M; Shastin, Aleksei V; Demidovich, Alexandra D; Shikhaliev, Namiq G; Magerramov, Abel M; Khrustalev, Victor N; Rakhimov, Rustem D; Vatsadze, Sergey Z

    2015-01-01

    Summary A new approach to ferrocenyl haloalkenes and bis-alkenes was elaborated. The key procedure involves copper catalyzed olefination of N-unsubstituted hydrazones, obtained from ferrocene-containing carbonyl compounds and hydrazine, with polyhaloalkanes. The procedure is simple, cheap and could be applied for the utilization of environmentally harmful polyhalocarbons. The cyclic voltammetry study of the representative examples of the synthesized ferrocenyl alkenes shows the strong dependence of the cathodic behavior on the amount of vinyl groups: while for the monoalkene containing molecules no reduction is seen, the divinyl products are reduced in several steps. PMID:26664627

  4. Stereoselective Synthesis of Saturated Heterocycles via Pd-Catalyzed Alkene Carboetherification and Carboamination Reactions

    PubMed Central

    Wolfe, John P.

    2009-01-01

    The development of Pd-catalyzed carboetherification and carboamination reactions between aryl/alkenyl halides and alkenes bearing pendant heteroatoms is described. These transformations effect the stereoselective construction of useful heterocycles such as tetrahydrofurans, pyrrolidines, imidazolidin-2-ones, isoxazolidines, and piperazines. The scope, limitations, and applications of these reactions are presented, and current stereochemical models are described. The mechanism of product formation, which involves an unusual intramolecular syn-insertion of an alkene into a Pd-Heteroatom bond is also discussed in detail. PMID:19183704

  5. Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides.

    PubMed

    Garlets, Zachary J; Parenti, Kaia R; Wolfe, John P

    2016-04-18

    The synthesis of cyclic sulfamides by enantioselective Pd-catalyzed alkene carboamination reactions between N-allylsulfamides and aryl or alkenyl bromides is described. High levels of asymmetric induction (up to 95:5 e.r.) are achieved using a catalyst composed of [Pd2 (dba)3 ] and (S)-Siphos-PE. Deuterium-labelling studies indicate the reactions proceed through syn-aminopalladation of the alkene and suggest that the control of syn- versus anti-aminopalladation pathways is important for asymmetric induction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Fe(III)/NaBH4-Mediated Free Radical Hydrofluorination of Unactivated Alkenes

    PubMed Central

    Barker, Timothy J.

    2012-01-01

    A powerful Fe(III)/NaBH4-mediated free radical hydrofluorination of unactivated alkenes is disclosed using Selectfluor as a source of fluorine and resulting in exclusive Markovnikov addition. In contrast to the traditional and unmanageable free radical hydrofluorination of alkenes, the Fe(III)/NaBH4-mediated reaction is conducted under exceptionally mild reaction conditions (0 °C, 5 min, CH3CN/H2O). The reaction can be conducted open to the air and with water as a cosolvent and demonstrates an outstanding substrate scope and functional group tolerance. PMID:22860624

  7. Homogeneous Pd-catalyzed transformation of terminal alkenes into primary allylic alcohols and derivatives.

    PubMed

    Tomita, Ren; Mantani, Kohei; Hamasaki, Akiyuki; Ishida, Tamao; Tokunaga, Makoto

    2014-08-04

    Synthesis of primary alcohols from terminal alkenes is an important process in both bulk and fine chemical syntheses. Herein, a homogeneous Pd-complex-catalyzed transformation of terminal alkenes into primary allylic alcohols, by using 5 mol % [Pd(PPh3)4] as a catalyst, and H2O, CO2, and quinone derivatives as reagents, is reported. When alcohols were used instead of H2O, allylic ethers were obtained. A proposed mechanism includes the addition of oxygen nucleophiles at the less-hindered terminal position of π-allyl Pd intermediates.

  8. Aerobic, Palladium-Catalyzed Dioxygenation of Alkenes Enabled by Catalytic Nitrite**

    PubMed Central

    Wickens, Zachary K.; Guzmán, Pablo E.; Grubbs, Robert H.

    2014-01-01

    Catalytic nitrite was found to enable carbon-oxygen bond-forming reductive elimination from unstable alkyl palladium intermediates, providing dioxygenated products from alkenes. A variety of functional groups are tolerated and high yields (up to 94%) are observed with many substrates, including a multi-gram scale reaction. Nitrogen dioxide, which could form from nitrite under the reaction conditions, was shown to be kinetically competent in the dioxygenation of alkenes. Furthermore, the reductive elimination event was probed with 18 O-labeling experiments, which demonstrated that both oxygen atoms in the difunctionalized products are derived from one molecule of acetic acid. PMID:25376666

  9. Reaction of Chlorosulfonyl Isocyanate (CSI) with Fluorosubstituted Alkenes: Evidence of a Concerted Pathway for Reaction of CSI with Fluorosubstituted Alkenes (Preprint)

    DTIC Science & Technology

    2010-06-01

    ABSTRACT Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with monofluoroalkenes. A vinyl fluorine atom on...SO2Cl R F O ‡ N SO2Cl F R O Abstract: Concerted reactions are indicated for the electrophilic addition of chlorosulfonyl isocyanate with...monofluoroalkenes. A vinyl fluorine atom on an alkene raises the energy of a step-wise transition state more than the energy of the competing concerted

  10. Modeling SOA formation from alkanes and alkenes in chamber experiments: effect of gas/wall partitioning of organic vapors.

    NASA Astrophysics Data System (ADS)

    Stéphanie La, Yuyi; Camredon, Marie; Ziemann, Paul; Ouzebidour, Farida; Valorso, Richard; Madronich, Sasha; Lee-Taylor, Julia; Hodzic, Alma; Aumont, Bernard

    2014-05-01

    Oxidation products of Intermediate Volatility Organic Compounds (IVOC) are expected to be the major precursors of secondary organic aerosols (SOA). Laboratory experiments were conducted this last decade in the Riverside APRC chamber to study IVOC oxidative mechanisms and SOA formation processes for a large set of linear, branched and cyclic aliphatic hydrocarbons (Ziemann, 2011). This dataset are used here to assess the explicit oxidation model GECKO-A (Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) (Aumont et al., 2005). The simulated SOA yields agree with the general trends observed in the chamber experiments. They are (i) increasing with the increasing carbon number; (ii) decreasing with increasing methyl branch number; and (iii) increasing for cyclic compounds compared to their corresponding linear analogues. However, simulated SOA yields are systematically overestimated regardless of the precursors, suggesting missing processes in the model. In this study, we assess whether gas-to-wall partitioning of organic vapors can explain these model/observation mismatches (Matsunaga and Ziemann, 2010). First results show that GECKO-A outputs better match the observations when wall uptake of organic vapors is taken into account. Effects of gas/wall partitioning on SOA yields and composition will be presented. Preliminary results suggest that wall uptake is a major process influencing SOA production in the Teflon chambers. References Aumont, B., Szopa, S., Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach. Atmos.Chem.Phys., 5, 2497-2517 (2005). P. J. Ziemann: Effects of molecular structure on the chemistry of aerosol formation from the OH-radical-initiated oxidation of alkanes and alkenes, Int. Rev.Phys.Chem., 30:2, 161-195 (2011). Matsunaga, A., Ziemann, P. J.: Gas-wall partitioning of organic compounds in a Teflon film

  11. Preference of Ruthenium-Based Metathesis Catalysts toward Z- and E-Alkenes as a Guide for Selective Reactions to Alkene Stereoisomers.

    PubMed

    Lee, Jihong; Kim, Kyung Hwan; Lee, Ok Suk; Choi, Tae-Lim; Lee, Hee-Seung; Ihee, Hyotcherl; Sohn, Jeong-Hun

    2016-09-02

    As a guide for selective reactions toward either Z- or E-alkene in a metathesis reaction, the relative preference of metathesis Ru catalysts for each stereoisomer was determined by a method using time-dependent fluorescence quenching. We found that Ru-1 prefers the Z-isomer over the E-isomer, whereas Ru-2 prefers the E-isomer over the Z-isomer. The Z/E-alkene preference of the catalysts precisely predicted the Z/E isomeric selectivity in the metathesis reactions of diene substrates possessing combinations of Z/E-alkenes. For the diene substrates, the rate order of the reactions using Ru-1 was Z,Z-1,6-diene > Z,E-1,6-diene > E,E-1,6-diene, while the completely opposite order of E,E-1,6-diene > Z,E-1,6-diene > Z,Z-1,6-diene was exhibited in the case of Ru-2.

  12. Cobalt-Catalyzed Enantioselective Hydrogenation of Minimally Functionalized Alkenes: Isotopic Labeling Provides Insight into the Origin of Stereoselectivity and Alkene Insertion Preferences.

    PubMed

    Friedfeld, Max R; Shevlin, Michael; Margulieux, Grant W; Campeau, Louis-Charles; Chirik, Paul J

    2016-03-16

    The asymmetric hydrogenation of cyclic alkenes lacking coordinating functionality with a C1-symmetric bis(imino)pyridine cobalt catalyst is described and has been applied to the synthesis of important substructures found in natural products and biologically active compounds. High activities and enantioselectivities were observed with substituted benzo-fused five-, six-, and seven-membered alkenes. The stereochemical outcome was dependent on both the ring size and exo/endo disposition. Deuterium labeling experiments support rapid and reversible 2,1-insertion that is unproductive for generating alkane product but accounts for the unusual isotopic distribution in deuterated alkanes. Analysis of the stereochemical outcome of the hydrogenated products coupled with isotopic labeling, stoichiometric, and kinetic studies established 1,2-alkene insertion as both turnover limiting and enantiodetermining with no evidence for erosion of cobalt alkyl stereochemistry by competing β-hydrogen elimination processes. A stereochemical model accounting for the preferred antipodes of the alkanes is proposed and relies on the subtle influence of the achiral aryl imine substituent on the cobalt catalyst.

  13. Biocatalytic Synthesis of Novel Partial Esters of a Bioactive Dihydroxy 4-Methylcoumarin by Rhizopus oryzae Lipase (ROL).

    PubMed

    Kumar, Vinod; Mathur, Divya; Srivastava, Smriti; Malhotra, Shashwat; Rana, Neha; Singh, Suraj K; Singh, Brajendra K; Prasad, Ashok K; Varma, Anjani J; Len, Christophe; Kuhad, Ramesh C; Saxena, Rajendra K; Parmar, Virinder S

    2016-11-09

    Highly regioselective acylation has been observed in 7,8-dihydroxy-4-methylcoumarin (DHMC) by the lipase from Rhizopus oryzae suspended in tetrahydrofuran (THF) at 45 °C using six different acid anhydrides as acylating agents. The acylation occurred regioselectively at one of the two hydroxy groups of the coumarin moiety resulting in the formation of 8-acyloxy-7-hydroxy-4-methylcoumarins, which are important bioactive molecules for studying biotansformations in animals, and are otherwise very difficult to obtain by only chemical steps. Six monoacylated, monohydroxy 4-methylcoumarins have been biocatalytically synthesised and identified on the basis of their spectral data and X-ray crystal analysis.

  14. Enzyme-functionalized polymer brush films on the inner wall of silicon-glass microreactors with tunable biocatalytic activity.

    PubMed

    Costantini, Francesca; Benetti, Edmondo M; Reinhoudt, David N; Huskens, Jurriaan; Vancso, G Julius; Verboom, Willem

    2010-12-21

    The lipase from Candida Rugosa was immobilized to a poly(methacrylic acid) polymer brush layer, grown on the inner wall of silicon-glass microreactors. The hydrolysis of 4-nitrophenyl acetate was used as a model reaction to study the activity of this biocatalytic system. The amount of bound lipase could be tuned by changing the polymerization time of the brush formation. The Michaelis-Menten constants and V(max) values, determined for immobilized and free lipase, are similar, demonstrating that the lipase's substrate affinity and its activity remain unchanged upon immobilization to the microchannel wall.

  15. Metallocene-catalyzed alkene polymerization and the observation of Zr-allyls.

    PubMed

    Landis, Clark R; Christianson, Matthew D

    2006-10-17

    Single-site polymerization catalysts enable exquisite control over alkene polymerization reactions to produce new materials with unique properties. Knowledge of catalyst speciation and fundamental kinetics are essential for full mechanistic understanding of zirconocene-catalyzed alkene polymerization. Currently the effect of activators on fundamental polymerization steps is not understood. Progress in understanding activator effects requires determination of fundamental kinetics for zirconocene catalysts with noncoordinating anions such as [B(C6F5)4]-. Kinetic NMR studies at low temperature demonstrate a very fast propagation rate for 1-hexene polymerization catalyzed by [(SBI)Zr(CH2SiMe3)][B(C6F5)4] [where SBI is rac-Me2Si(indenyl)2] with complete consumption of 1-hexene before the first NMR spectrum. Surprisingly, the first NMR spectrum reveals, aside from uninitiated catalyst, Zr-allyls as the sole catalyst-containing species. These Zr-allyls, which exist in two diastereomeric forms, have been characterized by physical and chemical methods. The mechanism of Zr-allyl formation was probed with a trapping experiment, leading us to favor a mechanism in which Zr-polymeryl undergoes beta-H transfer to metal without dissociation of coordinated alkene followed by sigma-bond metathesis to form H2 and Zr-allyl. Zr-allyl species undergo slow reactions with alkene but react rapidly with H2 to form hydrogenation products.

  16. Highly selective bis(imino)pyridine iron-catalyzed alkene hydroboration.

    PubMed

    Obligacion, Jennifer V; Chirik, Paul J

    2013-06-07

    Bis(imino)pyridine iron dinitrogen complexes have been shown to promote the anti-Markovnikov catalytic hydroboration of terminal, internal, and geminal alkenes with high activity and selectivity. The isolated iron dinitrogen compounds offer distinct advantages in substrate scope and overall performance over known precious metal catalysts and previously reported in situ generated iron species.

  17. Palladium-catalyzed highly regioselective hydroaminocarbonylation of aromatic alkenes to branched amides.

    PubMed

    Zhu, Jinping; Gao, Bao; Huang, Hanmin

    2017-03-22

    Pd(t-Bu3P)2 has been successfully identified as an efficient catalyst for the hydroaminocarbonylation of aromatic alkenes to branched amides under relatively mild reaction conditions. With hydroxylamine hydrochloride as an additive, both aliphatic and aromatic amines could be used as coupling partners for the present reaction, leading to production of branched amides in high yields with excellent regioselectivities.

  18. Continuous flow hydrogenation of nitroarenes, azides and alkenes using maghemite-Pd nanocomposites

    EPA Science Inventory

    Maghemite-supported ultra-fine Pd (1-2 nm) nanoparticles, prepared by a simple co-precipitation method, find application in the catalytic continuous flow hydrogenation of nitroarenes, azides, and alkenes wherein they play an important role in reduction of various functional group...

  19. Continuous flow hydrogenation of nitroarenes, azides and alkenes using maghemite-Pd nanocomposites

    EPA Science Inventory

    Maghemite-supported ultra-fine Pd (1-2 nm) nanoparticles, prepared by a simple co-precipitation method, find application in the catalytic continuous flow hydrogenation of nitroarenes, azides, and alkenes wherein they play an important role in reduction of various functional group...

  20. Tandem isomerization-decarboxylation for converting alkenoic fatty acids into alkenes

    USDA-ARS?s Scientific Manuscript database

    We report a facile Ru-catalyzed route to alkenes from alkenoic fatty acids via a readily accessible pre-catalyst [Ru(CO)2RCO2]n. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specif...

  1. Highly regio- and enantioselective multiple oxy- and amino-functionalizations of alkenes by modular cascade biocatalysis

    PubMed Central

    Wu, Shuke; Zhou, Yi; Wang, Tianwen; Too, Heng-Phon; Wang, Daniel I. C.; Li, Zhi

    2016-01-01

    New types of asymmetric functionalizations of alkenes are highly desirable for chemical synthesis. Here, we develop three novel types of regio- and enantioselective multiple oxy- and amino-functionalizations of terminal alkenes via cascade biocatalysis to produce chiral α-hydroxy acids, 1,2-amino alcohols and α-amino acids, respectively. Basic enzyme modules 1–4 are developed to convert alkenes to (S)-1,2-diols, (S)-1,2-diols to (S)-α-hydroxyacids, (S)-1,2-diols to (S)-aminoalcohols and (S)-α-hydroxyacids to (S)-α-aminoacids, respectively. Engineering of enzyme modules 1 & 2, 1 & 3 and 1, 2 & 4 in Escherichia coli affords three biocatalysts over-expressing 4–8 enzymes for one-pot conversion of styrenes to the corresponding (S)-α-hydroxyacids, (S)-aminoalcohols and (S)-α-aminoacids in high e.e. and high yields, respectively. The new types of asymmetric alkene functionalizations provide green, safe and useful alternatives to the chemical syntheses of these compounds. The modular approach for engineering multi-step cascade biocatalysis is useful for developing other new types of one-pot biotransformations for chemical synthesis. PMID:27297777

  2. Evolution of copper(II) as a new alkene amination promoter and catalyst

    PubMed Central

    Chemler, Sherry R.

    2010-01-01

    Copper(II) carboxylates and chiral copper(II) triflate·bis(oxazoline) complexes promote and catalyze intramolecular alkene carboamination, diamination and aminooxygenation reactions, creating an array of nitrogen heterocycles. High diastereoselectivity and enantioselectivity can be achieved in these transformations. This account reviews the discovery and development of these useful and interesting reactions. PMID:21379363

  3. Thiol-ene click chemistry: computational and kinetic analysis of the influence of alkene functionality.

    PubMed

    Northrop, Brian H; Coffey, Roderick N

    2012-08-22

    The influence of alkene functionality on the energetics and kinetics of radical initiated thiol-ene click chemistry has been studied computationally at the CBS-QB3 level. Relative energetics (ΔH°, ΔH(++), ΔG°, ΔG(++)) have been determined for all stationary points along the step-growth mechanism of thiol-ene reactions between methyl mercaptan and a series of 12 alkenes: propene, methyl vinyl ether, methyl allyl ether, norbornene, acrylonitrile, methyl acrylate, butadiene, methyl(vinyl)silanediamine, methyl crotonate, dimethyl fumarate, styrene, and maleimide. Electronic structure calculations reveal the underlying factors that control activation barriers for propagation and chain-transfer processes of the step-growth mechanism. Results are further extended to predict rate constants for forward and reverse propagation and chain-transfer steps (k(P), k(-P), k(CT), k(-CT)) and used to model overall reaction kinetics. A relationship between alkene structure and reactivity in thiol-ene reactions is derived from the results of kinetic modeling and can be directly related to the relative energetics of stationary points obtained from electronic structure calculations. The results predict the order of reactivity of alkenes and have broad implications for the use and applications of thiol-ene click chemistry.

  4. Synthetic trehalose esters of cis-alkene and diene α'-mycolic acids of Mycobacteria.

    PubMed

    Taher, Salam G; Muzael, Maged; Al Dulayymi, Juma'a R; Baird, Mark S

    2015-07-01

    The synthesis of an α'-mycolic acid of Mycobacterium smegmatis and other mycobacteria, containing a cis,cis-diene, and of the trehalose mono- and di-mycolates of this, and of a related α'-mycolic acid containing one cis-alkene, is reported. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  5. Pd-carbene migratory insertion: application to the synthesis of trifluoromethylated alkenes and dienes.

    PubMed

    Wang, Xi; Xu, Yan; Deng, Yifan; Zhou, Yujing; Feng, Jiajie; Ji, Guojing; Zhang, Yan; Wang, Jianbo

    2014-01-20

    Pd-catalyzed cross-coupling of halides with CF3-substituted diazo compounds or N-tosylhydrazones has been explored for the synthesis of CF3-substituted alkenes and 1,3-butadienes. Pd-carbene migratory insertion plays the key role in these transformations. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Lewis Acid-Promoted [2+2] Cycloadditions of Alkenes with Arylketenes

    PubMed Central

    Rigsbee, E. M.; Zhou, C.; Rasik, C. M.; Sptiz, A. Z.; Nichols, A. J.; Brown, M. K.

    2015-01-01

    A method for the [2+2] cycloaddition of arylketenes and alkenes is presented. The process involves the in situ generation of a ketene in the presence of a Lewis acid. The utility of products is demonstrated towards the synthesis of a common scaffold found in several natural product families. PMID:26419921

  7. Polymer enzyme conjugates as chiral ligands for sharpless dihydroxylation of alkenes in organic solvents.

    PubMed

    Konieczny, Stefan; Leurs, Melanie; Tiller, Joerg C

    2015-01-02

    Conjugates of enzymes and poly(2-methyloxazoline) were used as organosoluble amphiphilic polymer nanocontainers for dissolving osmate, thereby converting the enzymes into organosoluble artificial metalloenzymes. These were shown to catalyze the dihydroxylation of different alkenes with high enantioselectivity. The highest selectivities, found for osmate complexed with laccase polymer-enzyme conjugates (PECs), even exceed those of classical Sharpless catalysts.

  8. Torsional Control of Stereoselectivities in Electrophilic Additions and Cycloadditions to Alkenes

    PubMed Central

    Wang, Hao; Houk, K. N.

    2013-01-01

    Torsional effects control the π-facial stereoselectivities of a variety of synthetically important organic reactions. This review surveys theoretical calculations that have led to the understanding of the influence of the torsional effects on several types of stereoselective organic reactions, especially electrophilic additions and cycloadditions to alkenes. PMID:24409340

  9. One-Pot Anti-Markovnikov Hydroamination of Unactivated Alkenes by Hydrozirconation and Amination

    PubMed Central

    Strom, Alexandra E.

    2013-01-01

    A one-pot hydroamination of alkenes is reported. The synthesis of primary and secondary amines from unactivated olefins was accomplished in the presence of a variety of functional groups. Hydrozirconation, followed by amination with nitrogen electrophiles, provides exclusive anti-Markovnikov selectivity, and most products are isolated in high yields without the use of column chromatography. PMID:23899320

  10. OH yields in the gas-phase reactions of ozone with alkenes

    SciTech Connect

    Rickard, A.R.; Johnson, D.; McGill, C.D.; Marston, G.

    1999-09-23

    Hydroxyl radical yields are reported for the gas-phase ozonolyses of a range of alkenes. 1,3,5-Trimethylbenzene was employed as an OH tracer, and the diminution in its concentration was used to calculate OH yields by both a simple analytical kinetic expression and a numerically integrated model. The following OH yields were obtained, relative to alkene consumed: ethene (0.14), propene (0.32), 2-methylpropene (0.60), 2,3-dimethyl-2-butene (0.89), isoprene (0.44), {beta}-pinene (0.24), and {alpha}-pinene (0.83). A structure activity relationship (SAR) is presented for the estimation of OH yields based on structural moieties and reaction branching ratios. Reaction stoichiometries ({Delta}[alkene]/{Delta}[ozone]) are also reported, along with primary carbonyl yields measured in the presence and absence of excess SO{sub 2}, both under OH-free conditions. Reaction stoichiometries are shown to be correlated with alkene OH yields, and the mechanistic implications of this observation are discussed. The fractional increase in primary carbonyl yield in the presence of excess SO{sub 2} is shown to be inversely related to the OH yield and is interpreted as a measure of the fraction of the vibrationally excited Criegee intermediate that is stabilized in air at a pressure of 1 atm.

  11. Synthesis of insect pheromones belonging to the group of (Z)-trisubstituted alkenes

    NASA Astrophysics Data System (ADS)

    Grigorieva, Natalia Ya; Tsiklauri, Paata G.

    2000-07-01

    Stereo- and regiocontrolled methods for the construction of a (Z)-trisubstituted C=C bond and for the regiospecific introduction of a chiral fragment are exemplified in total syntheses of insect pheromones belonging to (Z)-trisubstituted alkenes. The bibliography includes 113 references.

  12. Biocatalytic desulfurization of thiophenic compounds and crude oil by newly isolated bacteria.

    PubMed

    Mohamed, Magdy El-Said; Al-Yacoub, Zakariya H; Vedakumar, John V

    2015-01-01

    Microorganisms possess enormous highly specific metabolic activities, which enable them to utilize and transform nearly every known chemical class present in crude oil. In this context, one of the most studied biocatalytic processes is the biodesulfurization (BDS) of thiophenic sulfur-containing compounds such as benzothiophene (BT) and dibenzothiophene (DBT) in crude oils and refinery streams. Three newly isolated bacterial strains, which were affiliated as Rhodococcus sp. strain SA11, Stenotrophomonas sp. strain SA21, and Rhodococcus sp. strain SA31, were enriched from oil contaminated soil in the presence of DBT as the sole S source. GC-FID analysis of DBT-grown cultures showed consumption of DBT, transient formation of DBT sulfone (DBTO2) and accumulation of 2-hydroxybiphenyl (2-HBP). Molecular detection of the plasmid-borne dsz operon, which codes for the DBT desulfurization activity, revealed the presence of dszA, dszB, and dszC genes. These results point to the operation of the known 4S pathway in the BDS of DBT. The maximum consumption rate of DBT was 11 μmol/g dry cell weight (DCW)/h and the maximum formation rate of 2-HBP formation was 4 μmol/g DCW/h. Inhibition of both cell growth and DBT consumption by 2-HBP was observed for all isolates but SA11 isolate was the least affected. The isolated biocatalysts desulfurized other model DBT alkylated homologs. SA11 isolate was capable of desulfurizing BT as well. Resting cells of SA11 exhibited 10% reduction in total sulfur present in heavy crude oil and 18% reduction in total sulfur present in the hexane-soluble fraction of the heavy crude oil. The capabilities of the isolated bacteria to survive and desulfurize a wide range of S compounds present in crude oil are desirable traits for the development of a robust BDS biocatalyst to upgrade crude oils and refinery streams.

  13. Highly enantioselective synthesis of γ-, δ-, and ε-chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)-Cu- or Pd-catalyzed cross-coupling.

    PubMed

    Xu, Shiqing; Oda, Akimichi; Kamada, Hirofumi; Negishi, Ei-ichi

    2014-06-10

    Despite recent advances of asymmetric synthesis, the preparation of enantiomerically pure (≥99% ee) compounds remains a challenge in modern organic chemistry. We report here a strategy for a highly enantioselective (≥99% ee) and catalytic synthesis of various γ- and more-remotely chiral alcohols from terminal alkenes via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction)-Cu- or Pd-catalyzed cross-coupling. ZACA-in situ oxidation of tert-butyldimethylsilyl (TBS)-protected ω-alkene-1-ols produced both (R)- and (S)-α,ω-dioxyfunctional intermediates (3) in 80-88% ee, which were readily purified to the ≥99% ee level by lipase-catalyzed acetylation through exploitation of their high selectivity factors. These α,ω-dioxyfunctional intermediates serve as versatile synthons for the construction of various chiral compounds. Their subsequent Cu-catalyzed cross-coupling with various alkyl (primary, secondary, tertiary, cyclic) Grignard reagents and Pd-catalyzed cross-coupling with aryl and alkenyl halides proceeded smoothly with essentially complete retention of stereochemical configuration to produce a wide variety of γ-, δ-, and ε-chiral 1-alkanols of ≥99% ee. The MαNP ester analysis has been applied to the determination of the enantiomeric purities of δ- and ε-chiral primary alkanols, which sheds light on the relatively undeveloped area of determination of enantiomeric purity and/or absolute configuration of remotely chiral primary alcohols.

  14. Highly enantioselective synthesis of γ-, δ-, and ε-chiral 1-alkanols via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA)–Cu- or Pd-catalyzed cross-coupling

    PubMed Central

    Xu, Shiqing; Oda, Akimichi; Kamada, Hirofumi; Negishi, Ei-ichi

    2014-01-01

    Despite recent advances of asymmetric synthesis, the preparation of enantiomerically pure (≥99% ee) compounds remains a challenge in modern organic chemistry. We report here a strategy for a highly enantioselective (≥99% ee) and catalytic synthesis of various γ- and more-remotely chiral alcohols from terminal alkenes via Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction)–Cu- or Pd-catalyzed cross-coupling. ZACA–in situ oxidation of tert-butyldimethylsilyl (TBS)-protected ω-alkene-1-ols produced both (R)- and (S)-α,ω-dioxyfunctional intermediates (3) in 80–88% ee, which were readily purified to the ≥99% ee level by lipase-catalyzed acetylation through exploitation of their high selectivity factors. These α,ω-dioxyfunctional intermediates serve as versatile synthons for the construction of various chiral compounds. Their subsequent Cu-catalyzed cross-coupling with various alkyl (primary, secondary, tertiary, cyclic) Grignard reagents and Pd-catalyzed cross-coupling with aryl and alkenyl halides proceeded smoothly with essentially complete retention of stereochemical configuration to produce a wide variety of γ-, δ-, and ε-chiral 1-alkanols of ≥99% ee. The MαNP ester analysis has been applied to the determination of the enantiomeric purities of δ- and ε-chiral primary alkanols, which sheds light on the relatively undeveloped area of determination of enantiomeric purity and/or absolute configuration of remotely chiral primary alcohols. PMID:24912191

  15. Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-substituted alkynes and bicyclic alkenes.

    PubMed

    Goodreid, Jordan; Villeneuve, Karine; Carlson, Emily; Tam, William

    2014-11-07

    Ruthenium-catalyzed asymmetric [2 + 2] cycloadditions between chiral acyl camphorsultam-functionalized alkynes and bicyclic alkenes were examined, providing adducts with complete exo stereoselectivity in good overall yield and enantioselectivity (up to 99% and 166:1, respectively), as well as appreciable diastereoselectivity (up to 163:1). The diastereoselectivity showed dependence on the solvent and temperature, as well as on the substitution pattern of the reacting alkyne and bicyclic alkene components. In general, higher diastereoselectivities were observed for reactions conducted in ethereal solvents and at lower temperatures between N-propynoyl camphorsultams and bicyclic alkenes.

  16. N-Heterocyclic Carbene Complexes in Oxidation Reactions

    NASA Astrophysics Data System (ADS)

    Jurčík, Václav; Cazin, Catherine S. J.

    This chapter describes applications of N-heterocyclic carbenes (NHCs) in oxidation chemistry. The strong σ-donation capabilities of the NHCs allow an efficient stabilisation of metal centres in high oxidation states, while high metal-NHC bond dissociation energies suppress their oxidative decomposition. These properties make NHCs ideal ligands for oxidation processes. The first part of this chapter is dedicated to the reactivity of NHC-metal complexes towards molecular oxygen whilst the second half highlights all oxidation reactions catalysed by such complexes. These include oxidation of alcohols and olefins, oxidative cyclisations, hydrations of alkynes and nitriles, oxidative cleavage of alkenes and the oxidation of methane.

  17. Copper-mediated cross-coupling-cyclization-oxidation: a one-pot reaction to construct polysubstituted pyrroles.

    PubMed

    Liu, Pei; Liu, Jin-ling; Wang, Heng-shan; Pan, Ying-ming; Liang, Hong; Chen, Zhen-Feng

    2014-05-14

    A novel and efficient procedure for the synthesis of polysubstituted pyrroles has been developed in this work. The polysubsituted pyrroles were synthesized directly from terminal alkenes, amines and β-keto esters through cross-coupling-cyclization-oxidation in the presence of a catalytic amount of cuprous chloride. This method provides a one-pot synthesis route from terminal alkenes to polysubstituted pyrroles for the first time and opens a new area in cuprous catalysis.

  18. The soluble methane mono-oxygenase of Methylococcus capsulatus (Bath). Its ability to oxygenate n-alkanes, n-alkenes, ethers, and alicyclic, aromatic and heterocyclic compounds.

    PubMed

    Colby, J; Stirling, D I; Dalton, H

    1977-08-01

    1. Methane mono-oxygenase of Methylococcus capsulatus (Bath) catalyses the oxidation of various substituted methane derivatives including methanol. 2. It is a very non-specific oxygenase and, in some of its catalytic properties, apparently resembles the analogous enzyme from Methylomonas methanica but differs from those found in Methylosinus trichosporium and Methylomonas albus. 3. CO is oxidized to CO2. 4. C1-C8 n-alkanes are hydroxylated, yielding mixtures of the corresponding 1- and 2-alcohols; no 3- or 4-alcohols are formed. 5. Terminal alkenes yield the corresponding 1,2-epoxides. cis- or trans-but-2-ene are each oxidized to a mixture of 2,3-epoxybutane and but-2-en-1-ol with retention of the cis or trans configuration in both products; 2-butanone is also formed from cis-but-2-ene only. 6. Dimethyl ether is oxidized. Diethyl ether undergoes sub-terminal oxidation, yielding ethanol and ethanal in equimolar amounts. 7. Methane mono-oxygenase also hydroxylates cyclic alkanes and aromatic compounds. However, styrene yields only styrene epoxide and pyridine yields only pyridine N-oxide. 8. Of those compounds tested, only NADPH can replace NADH as electron donor.

  19. The soluble methane mono-oxygenase of Methylococcus capsulatus (Bath). Its ability to oxygenate n-alkanes, n-alkenes, ethers, and alicyclic, aromatic and heterocyclic compounds.

    PubMed Central

    Colby, J; Stirling, D I; Dalton, H

    1977-01-01

    1. Methane mono-oxygenase of Methylococcus capsulatus (Bath) catalyses the oxidation of various substituted methane derivatives including methanol. 2. It is a very non-specific oxygenase and, in some of its catalytic properties, apparently resembles the analogous enzyme from Methylomonas methanica but differs from those found in Methylosinus trichosporium and Methylomonas albus. 3. CO is oxidized to CO2. 4. C1-C8 n-alkanes are hydroxylated, yielding mixtures of the corresponding 1- and 2-alcohols; no 3- or 4-alcohols are formed. 5. Terminal alkenes yield the corresponding 1,2-epoxides. cis- or trans-but-2-ene are each oxidized to a mixture of 2,3-epoxybutane and but-2-en-1-ol with retention of the cis or trans configuration in both products; 2-butanone is also formed from cis-but-2-ene only. 6. Dimethyl ether is oxidized. Diethyl ether undergoes sub-terminal oxidation, yielding ethanol and ethanal in equimolar amounts. 7. Methane mono-oxygenase also hydroxylates cyclic alkanes and aromatic compounds. However, styrene yields only styrene epoxide and pyridine yields only pyridine N-oxide. 8. Of those compounds tested, only NADPH can replace NADH as electron donor. PMID:411486

  20. 1,3-Diferuloyl-sn-glycerol from the biocatalytic transesterification of ethyl 4-hydroxy-3-methoxy cinnamic acid (ethyl ferulate) and soybean oil

    USDA-ARS?s Scientific Manuscript database

    1,3-Diferuloyl-sn-glycerol is a natural plant component found ubiquitously throughout the plant kingdom, possessing ultraviolet adsorbing and antioxidant properties. Diferuloyl glycerol was synthesized and isolated as a byproduct in up to 5% yield from the pilot plant scale packed-bed, biocatalytic...

  1. A new route to the synthesis of (E)- and (Z)-2-alkene-4-ynoates and nitriles from vic-iiodo-(E)-alkenes catalyzed by Pd(0) nanoparticles in water.

    PubMed

    Ranu, Brindaban C; Chattopadhyay, Kalicharan

    2007-06-07

    An efficient procedure for the stereoselective synthesis of (E)- and (Z)-2-alkene-4-ynoates and -nitriles by a simple reaction of vic-diiodo-(E)-alkenes with acrylic esters and nitriles catalyzed by in situ prepared Pd(0) nanoparticles in water has been developed. Addition of acrylic esters leads to (E)-isomers exclusively, whereas (Z)-isomers are obtained in high stereoselectivity from reactions of acrylonitrile. The aqueous slurry of Pd nanoparticles is recycled. A probable mechanism has been suggested.

  2. The significance of the alkene size and the nature of the metal ion in metal-alkene complexes: a theoretical study.

    PubMed

    Premkumar, J Richard; Vijay, Dolly; Sastry, G Narahari

    2012-04-28

    Cation interactions with π-systems are a problem of outstanding contemporary interest and the nature of these interactions seems to be quite different for transition and main group metal ions. In this paper, we have systematically analyzed the contrast in the bonding of Cu(+) and main group metal ions. The molecular structures and energetics of the complexes formed by various alkenes (A = C(n)H(2n), n = 2-6; C(n)H(2n- 2), n = 3-8 and C(n)H(2n + 2), n = 5-10) and metal ions (M = Li(+), Na(+), K(+), Ca(2+), Mg(2+), Cu(+) and Zn(2+)) are investigated by employing ab initio post Hartree-Fock (MP2/6-311++G**) calculations and are reported in the current study. The study, which also aims to evaluate the effect of the size of the alkyl portion attached to the π-system on the complexation energy, indicates a linear relationship between the two. The decreasing order of complexation energy with various metal ion-alkene complexes follows the order Zn(2+)-A > Mg(2+)-A > Ca(2+)-A > Cu(+)-A > Li(+)-A > Na(+)-A > K(+)-A. The increased charge transfer and the electron density at (3,-1) intermolecular bond critical point corroborates well with the size of the π-system and the complexation energy. The observed deviation from the linear dependency of the Cu(+)-A complexes is attributed to the dπ→π* back bonding interaction. An energy decomposition analysis via the reduced variational space (RVS) procedure was also carried out to analyze which component among polarization, charge transfer, coulomb and exchange repulsion contributes to the increase in the complexation energy. The RVS results suggest that the polarization component significantly contributes to the increase in the complexation energy when the alkene size increases. This journal is © The Royal Society of Chemistry 2012

  3. In situ generated bulky palladium hydride complexes as catalysts for the efficient isomerization of olefins. Selective transformation of terminal alkenes to 2-alkenes.

    PubMed

    Gauthier, Delphine; Lindhardt, Anders T; Olsen, Esben P K; Overgaard, Jacob; Skrydstrup, Troels

    2010-06-16

    Application of an in situ generated bulky palladium(II) hydride catalyst obtained from a 1:1:1 mixture of Pd(dba)(2), P(tBu)(3), and isobutyryl chloride provides an efficient protocol for the isomerization and migration of a variety of olefins. In addition to the isomerization of (Z)- to (E)-olefins, the conjugative migration of allylbenzenes, allyl ethers, and amines was effectively achieved in near-quantitative yields and with excellent functional group tolerance. Catalyst loadings in the range of 0.5-1.0 mol % were typically applied, but even loadings as low as 0.25 mol % could be achieved when the reactions were performed under neat conditions. More interestingly, the investigated catalyst proved to be selective for converting terminal alkenes to 2-alkenes. This one-carbon migration process for monosubstituted olefins provides an alternative catalyst, which bridges the gap between the allylation and propenylation/vinylation protocols. Several substrates, including homoallylic alcohols and amines, were selectively transformed into their corresponding 2-alkenes, and examples using enantiomerically enriched substrates provided products without epimerization at the allylic stereogenic carbon centers. Finally, some mechanistic investigations were undertaken to understand the nature of the active in situ generated Pd-H catalyst. These studies revealed that the catalytic system is highly dependent on the large steric demand of the P(tBu)(3) ligand. The use of an alternative ligand, cataCXium PinCy, also proved effective for generating an active catalyst, and it was demonstrated in some cases to display better selectivity for the one-carbon shifts of terminal olefins. A possible intermediate involved in the preparation of the active catalyst was characterized by its single-crystal X-ray structure, which revealed a monomeric tricoordinated palladium(II) acyl complex, bearing a chloride ligand.

  4. Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes.

    PubMed

    Key, Hanna M; Dydio, Paweł; Liu, Zhennan; Rha, Jennifer Y-E; Nazarenko, Andrew; Seyedkazemi, Vida; Clark, Douglas S; Hartwig, John F

    2017-04-26

    Enzymes catalyze organic transformations with exquisite levels of selectivity, including chemoselectivity, stereoselectivity, and substrate selectivity, but the types of reactions catalyzed by enzymes are more limited than those of chemical catalysts. Thus, the convergence of chemical catalysis and biocatalysis can enable enzymatic systems to catalyze abiological reactions with high selectivity. Recently, we disclosed artificial enzymes constructed from the apo form of heme proteins and iridium porphyrins that catalyze the insertion of carbenes into a C-H bond. We postulated that the same type of Ir(Me)-PIX enzymes could catalyze the cyclopropanation of a broad range of alkenes with control of multiple modes of selectivity. Here, we report the evolution of artificial enzymes that are highly active and highly stereoselective for the addition of carbenes to a wide range of alkenes. These enzymes catalyze the cyclopropanation of terminal and internal, activated and unactivated, electron-rich and electron-deficient, conjugated and nonconjugated alkenes. In particular, Ir(Me)-PIX enzymes derived from CYP119 catalyze highly enantio- and diastereoselective cyclopropanations of styrene with ±98% ee, >70:1 dr, >75% yield, and ∼10,000 turnovers (TON), as well as 1,2-disubstituted styrenes with up to 99% ee, 35:1 dr, and 54% yield. Moreover, Ir(Me)-PIX enzymes catalyze cyclopropanation of internal, unactivated alkenes with up to 99% stereoselectivity, 76% yield, and 1300 TON. They also catalyze cyclopropanation of natural products with diastereoselectivities that are complementary to those attained with standard transition metal catalysts. Finally, Ir(Me)-PIX P450 variants react with substrate selectivity that is reminiscent of natural enzymes; they react preferentially with less reactive internal alkenes in the presence of more reactive terminal alkenes. Together, the studies reveal the suitability of Ir-containing P450s to combine the broad reactivity and substrate scope

  5. QUANTIFICATION OF FUGITIVE REACTIVE ALKENE EMISSIONS FROM PETROCHEMICAL PLANTS WITH PERFLUOROCARBON TRACERS.

    SciTech Connect

    SENUM,G.I.; DIETZ,R.N.

    2004-06-30

    Recent studies demonstrate the impact of fugitive emissions of reactive alkenes on the atmospheric chemistry of the Houston Texas metropolitan area (1). Petrochemical plants located in and around the Houston area emit atmospheric alkenes, such as ethene, propene and 1,3-butadiene. The magnitude of emissions is a major uncertainty in assessing their effects. Even though the petrochemical industry reports that fugitive emissions of alkenes have been reduced to less than 0.1% of daily production, recent measurement data, obtained during the TexAQS 2000 experiment indicates that emissions are perhaps a factor of ten larger than estimated values. Industry figures for fugitive emissions are based on adding up estimated emission factors for every component in the plant to give a total estimated emission from the entire facility. The dramatic difference between estimated and measured rates indicates either that calculating emission fluxes by summing estimates for individual components is seriously flawed, possibly due to individual components leaking well beyond their estimated tolerances, that not all sources of emissions for a facility are being considered in emissions estimates, or that there are known sources of emissions that are not being reported. This experiment was designed to confirm estimates of reactive alkene emissions derived from analysis of the TexAQS 2000 data by releasing perfluorocarbon tracers (PFTs) at a known flux from a petrochemical plant and sampling both the perfluorocarbon tracer and reactive alkenes downwind using the Piper-Aztec research aircraft operated by Baylor University. PFTs have been extensively used to determine leaks in pipelines, air infiltration in buildings, and to characterize the transport and dispersion of air parcels in the atmosphere. Over 20 years of development by the Tracer Technology Center (TTC) has produced a range of analysis instruments, field samplers and PFT release equipment that have been successfully deployed in a

  6. A simple and facile Heck-type arylation of alkenes with diaryliodonium salts using magnetically recoverable Pd-catalyst

    EPA Science Inventory

    The Heck-type arylation of alkenes was achieved in aqueous polyethylene glycol using a magnetically recoverable heterogenized palladium catalyst employing diaryliodonium salts under ambient conditions. The benign reaction medium and the stability of the catalyst are the salient f...

  7. Arylation and vinylation of alkenes based on unusual sequential semipinacol rearrangement/Grob fragmentation of allylic alcohols.

    PubMed

    Yuan, Dao-Yi; Tu, Yong-Qiang; Fan, Chun-An

    2008-10-03

    Alkenes can be stereoselectively arylated and vinylated without transition-metal catalyst under mild conditions through an interesting NBS-promoted semipinacol rearrangement and a subsequent unusual NaOH-mediated Grob fragmentation.

  8. A simple and facile Heck-type arylation of alkenes with diaryliodonium salts using magnetically recoverable Pd-catalyst

    EPA Science Inventory

    The Heck-type arylation of alkenes was achieved in aqueous polyethylene glycol using a magnetically recoverable heterogenized palladium catalyst employing diaryliodonium salts under ambient conditions. The benign reaction medium and the stability of the catalyst are the salient f...

  9. Pressure-Dependent Criegee Intermediate Stabilization from Alkene Ozonolysis.

    PubMed

    Hakala, Jani P; Donahue, Neil M

    2016-04-14

    We explored the pressure dependence of acetone oxide (stabilized Criegee Intermediate, sCI) formation from 2,3-dimethyl-2-butene ozonolysis between 50 and 900 Torr using a new, highly accurate technique. We exploited the ability of the sCI to oxidize SO2 to H2SO4, which we measured with a chemical ionization mass spectrometer. We produced the Criegee intermediates (CI) in a high-pressure flow reactor via ozonolysis of 2,3-dimethyl-2-butene (tetramethyl ethylene, TME) and measured the relative H2SO4 concentrations with and without an added OH scavenger. Because the TME reaction with ozone forms acetone oxide (a syn-CI) with unit efficiency, we directly calculated the sCI yields at different pressures from the precisely measured ratio of the uncalibrated H2SO4 signal with and without the scavenger. We observed a linear pressure dependence between 50 and 900 Torr with a minimum stabilization of 12.7 ± 0.6% at 50 Torr and a maximum stabilization of 42 ± 2% at 900 Torr. A linear fit to the measured data points shows a zero-pressure intercept of 15 ± 2%, constraining the fraction of CI formed below the barrier for acetone oxide isomerization.

  10. Engineering the microstructure and permeability of thin multilayer latex biocatalytic coatings containing E. coli.

    PubMed

    Lyngberg, O K; Ng, C P; Thiagarajan, V; Scriven, L E; Flickinger, M C

    2001-01-01

    The microstructure and permeability of rehydrated 20-100 microm thick partially coalesced (vinyl-actetate acrylic copolymer) SF091 latex coatings and a 118 microm thick model trilayer biocatalytic coating consisting of two sealant SF091 layers containing a middle layer of viable E. coli HB101 + latex were studied as delaminated films in a diffusion apparatus with KNO(3) as the diffussant. The permeability of the hydrated coatings is due to diffusive transport through the pore space between the partially coalesced SF091 latex particles. Coating microstructure was visualized by fast freeze cryogenic scanning electron microscopy (cryo-SEM). The effective diffusion coefficient of SF091 latex coatings (diffusive permeability/film thickness) was determined as the ratio of the effective diffusivity of KNO(3) to its diffusivity in water (D(eff)/D). Polymer particle coalescence was arrested by two methods to increase coating permeability. The first used glycerol with coating drying at 4 degrees C, near the glass transition temperature (T(g)). The second method used sucrose or trehalose as a filler to arrest coalescence; the filler was then dissolved away. D(eff)/D was measured as a function of film thickness; content of glycerol, sucrose, and trehalose; drying time; and rehydration time. D(eff)/D varied from 3 x 10(-4) for unmodified SF091 coatings to 6.8 x 10(-2) for coatings containing sucrose. D(eff)/D was reduced by the flattening of latex particles against the surface of the solid substrate, as well as by the presence of the colloid stabilizer hydroxyethylcellulose (HEC). When corrected for the flattened particle layer, D(eff)/D of HEC-free coatings was as high as 0.20, which agreed with the value predicted from analysis of cryo-SEM images of the coat surface. D(eff)/D decreased by one-half in approximately 5 days in rehydrated SF091 coatings, indicating that significant wet coalescence occurs after glycerol, sucrose, or trehalose are leached from the films. D

  11. Iron(III)/NaBH4-Mediated Additions to Unactivated Alkenes: Synthesis of Novel 20′-Vinblastine Analogues

    PubMed Central

    Leggans, Erick K.; Barker, Timothy J.; Duncan, Katharine K.; Boger, Dale L.

    2012-01-01

    An Fe(III)/NaBH4-mediated reaction for the functionalization of unactivated alkenes is described defining the alkene substrate scope, establishing the exclusive Markovnikov addition, exploring a range of free radical traps, examining the Fe(III) salt and initiating hydride source, introducing H2O-cosolvent mixtures, and exploring catalytic variants. Its use led to the preparation of a novel, potent and previously inaccessible C20′-vinblastine analogue. PMID:22369097

  12. Mechanistic interpretation of selective catalytic hydrogenation and isomerization of alkenes and dienes by ligand deactivated Pd nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhu, Jie S.; Shon, Young-Seok

    2015-10-01

    Unsupported thiolate-capped palladium nanoparticle catalysts are found to be highly substrate-selective for alkene hydrogenation and isomerization. Steric and poisoning effects from thiolate ligands on the nanoparticle surface control reactivity and selectivity by influencing alkene adsorption and directing either di-σ or mono-σ bond formation. The presence of overlapping p orbitals and α protons in alkenes greatly influences the catalytic properties of deactivated palladium nanoparticles leading to easily predictable hydrogenation or isomerization products.Unsupported thiolate-capped palladium nanoparticle catalysts are found to be highly substrate-selective for alkene hydrogenation and isomerization. Steric and poisoning effects from thiolate ligands on the nanoparticle surface control reactivity and selectivity by influencing alkene adsorption and directing either di-σ or mono-σ bond formation. The presence of overlapping p orbitals and α protons in alkenes greatly influences the catalytic properties of deactivated palladium nanoparticles leading to easily predictable hydrogenation or isomerization products. Electronic supplementary information (ESI) available: Supplementary figures, methods, materials, and characterization data. See DOI: 10.1039/c5nr05090a

  13. Potential roles of myeloperoxidase and hypochlorous acid in metabolism and toxicity of alkene hydrocarbons and drug molecules containing olefinic moieties.

    PubMed

    Zhang, Xin-Yu; Elfarra, Adnan A

    2017-05-01

    Adverse drug reactions (ADRs) pose a significant health problem and are generally attributed to reactive metabolites. Olefinic moieties in drugs can undergo cytochrome P450-mediated bioactivation to produce reactive metabolites but myeloperoxidase (MPO)-mediated bioactivation of these moieties has not been reported. Thus, small molecules of alkene hydrocarbons are used as model compounds to characterize the MPO-mediated metabolism. Areas covered: The authors focus on MPO-mediated metabolism of alkene hydrocarbons to form chlorohydrins and the potential role of chlorohydrins in alkene toxicity and carcinogenicity. A case study is presented, in which a carcinogenic alkene, 1,3-butadiene, is demonstrated to form 1-chloro-2-hydroxy-3-butene (CHB) through the MPO-mediated pathway. Further bioactivation of CHB yields a cross-linking metabolite, 1-chloro-3-buten-2-one (CBO), which is highly reactive toward glutathione, proteins, nucleosides, and DNA. Toxicity and mutagenicity of CHB and CBO are also presented. Expert opinion: Alkene hydrocarbons readily undergo MPO-mediated bioactivation to form chlorohydrins, which can further be biotransformed into proteins/DNA-modifying reactive metabolites. Therefore, chlorohydrin formation may play an important role in alkene toxicity and carcinogenicity. Olefinic moieties in drugs are expected to undergo similar bioactivation, which may contribute to ADRs. Studies to investigate the roles of MPO and chlorohydrin formation in ADRs are thus warranted.

  14. The effect of 1-alkene addition on hydrocarbon product distribution in Fischer-Tropsch synthesis on a cobalt catalyst

    SciTech Connect

    Yates, I.C.; Satterfield, C.N.

    1991-07-01

    The cobalt-catalyzed reactions of C{sub 2}H{sub 4}, C{sub 3}H{sub 6}, or 1-C{sub 4}H{sub 8} added to synthesis gas in concentrations ranging from 0.5 to 1.2 mol. % of total feed were studied at 220{degrees}C, and 0.45 to 1.48 MPa. H{sub 2}/CO feed ratios were varied between 1.45 to 2.25 and H{sub 2} + CO conversions between 5 and 30% were observed. 1-Alkenes incorporate into growing chains on the catalyst surface, probably by initiating and/or terminating the chain growth process. Only ethene may propagate chain growth significantly. The propensity of the 1-alkenes to incorporate decreases with increasing carbon number of the 1-alkene and is affected by the extent of competitive reactions, notably hydrogenation to the alkene and isomerization to the 2-alkene. Incorporation is most evident in products above about C{sub 10}+. The double-{alpha} behavior exhibited by most Fischer-Tropsch catalysts can be interpreted as the sum of two growth processes, one a stepwise single-carbon growth process and the other a 1-alkene incorporation process. Many of the effects of process variables on the hydrocarbon selectivity of Fischer-Tropsch catalysts are consistent with this theory. 14 refs., 10 figs., 1 tab.

  15. Postpolymerization Modifications of Alkene-Functional Polycarbonates for the Development of Advanced Materials Biomaterials.

    PubMed

    Thomas, Anthony W; Dove, Andrew P

    2016-12-01

    Functional aliphatic polycarbonates have attracted significant attention as materials for use as biomedical polymers in recent years. The incorporation of pendent functionality offers a facile method of modifying materials postpolymerization, thus enabling functionalities not compatible with ring-opening polymerization (ROP) to be introduced into the polymer. In particular, polycarbonates bearing alkene-terminated functional groups have generated considerable interest as a result of their ease of synthesis, and the wide range of materials that can be obtained by performing simple postpolymerization modifications on this functionality, for example, through radical thiol-ene addition, Michael addition, and epoxidation reactions. This review presents an in-depth appraisal of the methods used to modify alkene-functional polycarbonates postpolymerization, and the diversity of practical applications for which these materials and their derivatives have been used. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Unsymmetrical E-Alkenes from the Stereoselective Reductive Coupling of Two Aldehydes.

    PubMed

    Esfandiarfard, Keyhan; Mai, Juri; Ott, Sascha

    2017-03-01

    The unprecedented formation of unsymmetrical alkenes from the intermolecular reductive coupling of two different aldehydes is described. In contrast to the McMurry reaction which affords statistical product mixtures, selectivity in the reported procedure is achieved by a sequential ionic mechanism in which a first aldehyde is reacted with a phosphanylphosphonate to afford a phosphaalkene intermediate which, upon activation by hydroxide, reacts with a second aldehyde to the unsymmetrical E-alkenes. The described reaction is free of transition metals and proceeds under ambient temperature within minutes in good to excellent overall yields. It is a new methodology to use feedstock aldehydes for the direct production of C═C double bond-containing products and may impact how chemists think of multistep synthetic sequences in the future.

  17. Development of Novel Alkene Oxindole Derivatives As Orally Efficacious AMP-Activated Protein Kinase Activators

    PubMed Central

    2013-01-01

    Adenosine 5′-monophosphate-activated protein kinase (AMPK) is emerging as a promising drug target for its regulatory function in both glucose and lipid metabolism. Compound PT1 (5) was originally identified from high throughput screening as a small molecule activator of AMPK through the antagonization of the autoinhibition in α subunits. In order to enhance its potency at AMPK and bioavailability, structure–activity relationship studies have been performed and resulted in a novel series of AMPK activators based on an alkene oxindole scaffold. Following their evaluation in pharmacological AMPK activation assays, lead compound 24 was identified to possess improved potency as well as favorable pharmacokinetic profile. In the diet-induced obesity (DIO) mouse model, compound 24 was found to improve glucose tolerance and alleviate insulin resistance. The in vitro and in vivo data for these alkene oxindoles warrant further studies for their potential therapeutic medications in metabolic associated diseases. PMID:24900695

  18. Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source.

    PubMed

    Kawamura, Shintaro; Sodeoka, Mikiko

    2016-07-18

    An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal-free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp(3) carbon to construct synthetically useful skeletons. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Hyperfine frequency shift and Zeeman relaxation in alkali-metal-vapor cells with antirelaxation alkene coating

    NASA Astrophysics Data System (ADS)

    Corsini, Eric P.; Karaulanov, Todor; Balabas, Mikhail; Budker, Dmitry

    2013-02-01

    An alkene-based antirelaxation coating for alkali-metal vapor cells exhibiting Zeeman relaxation times up to 77 s was recently identified by Balabas The long relaxation times, two orders of magnitude longer than in paraffin- (alkane-) coated cells, motivate revisiting the question of what the mechanism is underlying wall-collision-induced relaxation and renew interest in applications of alkali-metal vapor cells to secondary frequency standards. We measure the width and frequency shift of the ground-state hyperfine mF=0→mF'=0 transition (clock resonance) in vapor cells with 85Rb and 87Rb atoms, with an alkene antirelaxation coating. We find that the frequency shift is slightly larger than for paraffin-coated cells and that the Zeeman linewidth scales linearly with the hyperfine frequency shift.

  20. Decarboxylation of fatty acids to terminal alkenes by cytochrome P450 compound I.

    PubMed

    Grant, Job L; Hsieh, Chun H; Makris, Thomas M

    2015-04-22

    OleT(JE), a cytochrome P450, catalyzes the conversion of fatty acids to terminal alkenes using hydrogen peroxide as a cosubstrate. Analytical studies with an eicosanoic acid substrate show that the enzyme predominantly generates nonadecene and that carbon dioxide is the one carbon coproduct of the reaction. The addition of hydrogen peroxide to a deuterated substrate-enzyme (E-S) complex results in the transient formation of an iron(IV) oxo π cation radical (Compound I) intermediate which is spectroscopically indistinguishable from those that perform oxygen insertion chemistries. A kinetic isotope effect for Compound I decay suggests that it abstracts a substrate hydrogen atom to initiate fatty acid decarboxylation. Together, these results indicate that the initial mechanism for alkene formation, which does not result from oxygen rebound, is similar to that widely suggested for P450 monooxygenation reactions.