Medium chain and behenic acid incorporated structured lipids from sal, mango and kokum fats by lipase acidolysis.

PubMed

Bebarta, Biranchi; M, Jhansi; Kotasthane, Pranitha; Sunkireddy, Yella Reddy

2013-01-15

Medium chain (MC) and behenic fatty acids were incorporated into kokum, sal and mango fats using 1,3-specific lipase catalysed acidolysis. The incorporation of fatty acids increased with increase in concentration of fatty acids and duration of reaction. The order of incorporation of fatty acids was C22:0>C10:0>C8:0, to the extent of 53%, 42.5%, 35.8%, respectively, after 16 h, using kokum as substrate. The same trend was observed with sal or mango fats as substrates though the percentages incorporated were different. The modified products with higher contents of MC were liquids with no solid fats, even at 0°C, and which showed low cloud point due to an increase in triacylglycerols containing lower chain fatty acids. The modified products after incorporating both MC and C22:0 showed long melting ranges and were suitable for use in bakery, confectionery, etc. as vanaspati substitutes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Final Report: Investigation of Catalytic Pathways for Lignin Breakdown into Monomers and Fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gluckstein, Jeffrey A; Hu, Michael Z.; Kidder, Michelle

2010-12-01

Lignin is a biopolymer that comprises up to 35% of woody biomass by dry weight. It is currently underutilized compared to cellulose and hemicellulose, the other two primary components of woody biomass. Lignin has an irregular structure of methoxylated aromatic groups linked by a suite of ether and alkyl bonds which makes it difficult to degrade selectively. However, the aromatic components of lignin also make it promising as a base material for the production of aromatic fuel additives and cyclic chemical feed stocks such as styrene, benzene, and cyclohexanol. Our laboratory research focused on three methods to selectively cleave andmore » deoxygenate purified lignin under mild conditions: acidolysis, hydrogenation and electrocatalysis. (1) Acidolysis was undertaken in CH2Cl2 at room temperature. (2) Hydrogenation was carried out by dissolving lignin and a rhodium catalyst in 1:1 water:methoxyethanol under a 1 atm H2 environment. (3) Electrocatalysis of lignin involved reacting electrically generated hydrogen atoms at a catalytic palladium cathode with lignin dissolved in a solution of aqueous methanol. In all of the experiments, the lignin degradation products were identified and quantified by gas chromatography mass spectroscopy and flame ionization detection. Yields were low, but this may have reflected the difficulty in recovering the various fractions after conversion. The homogeneous hydrogenation of lignin showed fragmentation into monomers, while the electrocatalytic hydrogenation showed production of polyaromatic hydrocarbons and substituted benzenes. In addition to the experiments, promising pathways for the conversion of lignin were assessed. Three conversion methods were compared based on their material and energy inputs and proposed improvements using better catalyst and process technology. A variety of areas were noted as needing further experimental and theoretical effort to increase the feasibility of lignin conversion to fuels.« less

Eco-friendly streamlined process for sporopollenin exine capsule extraction

PubMed Central

Mundargi, Raghavendra C.; Potroz, Michael G.; Park, Jae Hyeon; Seo, Jeongeun; Tan, Ee-Lin; Lee, Jae Ho; Cho, Nam-Joon

2016-01-01

Sporopollenin exine capsules (SECs) extracted from Lycopodium clavatum spores are an attractive biomaterial possessing a highly robust structure suitable for microencapsulation strategies. Despite several decades of research into SEC extraction methods, the protocols commonly used for L. clavatum still entail processing with both alkaline and acidolysis steps at temperatures up to 180 °C and lasting up to 7 days. Herein, we demonstrate a significantly streamlined processing regimen, which indicates that much lower temperatures and processing durations can be used without alkaline lysis. By employing CHN elemental analysis, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), and dynamic image particle analysis (DIPA), the optimum conditions for L. clavatum SEC processing were determined to include 30 hours acidolysis at 70 °C without alkaline lysis. Extending these findings to proof-of-concept encapsulation studies, we further demonstrate that our SECs are able to achieve a loading of 0.170 ± 0.01 g BSA per 1 g SECs by vacuum-assisted loading. Taken together, our streamlined processing method and corresponding characterization of SECs provides important insights for the development of applications including drug delivery, cosmetics, personal care products, and foods. PMID:26818918

Eco-friendly streamlined process for sporopollenin exine capsule extraction

NASA Astrophysics Data System (ADS)

Mundargi, Raghavendra C.; Potroz, Michael G.; Park, Jae Hyeon; Seo, Jeongeun; Tan, Ee-Lin; Lee, Jae Ho; Cho, Nam-Joon

2016-01-01

Sporopollenin exine capsules (SECs) extracted from Lycopodium clavatum spores are an attractive biomaterial possessing a highly robust structure suitable for microencapsulation strategies. Despite several decades of research into SEC extraction methods, the protocols commonly used for L. clavatum still entail processing with both alkaline and acidolysis steps at temperatures up to 180 °C and lasting up to 7 days. Herein, we demonstrate a significantly streamlined processing regimen, which indicates that much lower temperatures and processing durations can be used without alkaline lysis. By employing CHN elemental analysis, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM), and dynamic image particle analysis (DIPA), the optimum conditions for L. clavatum SEC processing were determined to include 30 hours acidolysis at 70 °C without alkaline lysis. Extending these findings to proof-of-concept encapsulation studies, we further demonstrate that our SECs are able to achieve a loading of 0.170 ± 0.01 g BSA per 1 g SECs by vacuum-assisted loading. Taken together, our streamlined processing method and corresponding characterization of SECs provides important insights for the development of applications including drug delivery, cosmetics, personal care products, and foods.

Structure-guided modification of Rhizomucor miehei lipase for production of structured lipids.

PubMed

Zhang, Jun-Hui; Jiang, Yu-Yan; Lin, Ying; Sun, Yu-Fei; Zheng, Sui-Ping; Han, Shuang-Yan

2013-01-01

To improve the performance of yeast surface-displayed Rhizomucor miehei lipase (RML) in the production of human milk fat substitute (HMFS), we mutated amino acids in the lipase substrate-binding pocket based on protein hydrophobicity, to improve esterification activity. Five mutants: Asn87Ile, Asn87Ile/Asp91Val, His108Leu/Lys109Ile, Asp256Ile/His257Leu, and His108Leu/Lys109Ile/Asp256Ile/His257Leu were obtained and their hydrolytic and esterification activities were assayed. Using Discovery Studio 3.1 to build models and calculate the binding energy between lipase and substrates, compared to wild-type, the mutant Asp256Ile/His257Leu was found to have significantly lower energy when oleic acid (3.97 KJ/mol decrease) and tripalmitin (7.55 KJ/mol decrease) were substrates. This result was in accordance with the esterification activity of Asp256Ile/His257Leu (2.37-fold of wild-type). The four mutants were also evaluated for the production of HMFS in organic solvent and in a solvent-free system. Asp256Ile/His257Leu had an oleic acid incorporation of 28.27% for catalyzing tripalmitin and oleic acid, and 53.18% for the reaction of palm oil with oleic acid. The efficiency of Asp256Ile/His257Leu was 1.82-fold and 1.65-fold that of the wild-type enzyme for the two reactions. The oleic acid incorporation of Asp256Ile/His257Leu was similar to commercial Lipozyme RM IM for palm oil acidolysis with oleic acid. Yeast surface-displayed RML mutant Asp256Ile/His257Leu is a potential, economically feasible catalyst for the production of structured lipids.

Candida rugosa lipase LIP1-catalyzed transesterification to produce human milk fat substitute.

PubMed

Srivastava, Anita; Akoh, Casimir C; Chang, Shu-Wei; Lee, Guan-Chiun; Shaw, Jei-Fu

2006-07-12

Structured lipids (SLs) containing palmitic and oleic acids were synthesized by transesterification of tripalmitin with either oleic acid or methyl oleate as acyl donor. This SL with palmitic acid at the sn-2 position and oleic acid at sn-1,3 positions is similar in structure to human milk fat triacylglycerol. LIP1, an isoform of Candida rugosa lipase (CRL), was used as biocatalyst. The effects of reaction temperature, substrate molar ratio, and time on incorporation of oleic acid were investigated. Reaction time and temperature were set at 6, 12, and 24 h, and 35, 45, and 55 degrees C, respectively. Substrate molar ratio was varied from 1:1 to 1:4. The highest incorporation of oleic acid (37.7%) was at 45 degrees C with methyl oleate as acyl donor. Oleic acid resulted in slightly lesser (26.3%) incorporation. Generally, higher percentage incorporation of oleic acid was observed with methyl oleate (transesterification) than with oleic acid (acidolysis). In both cases percentage incorporation increased with reaction time. Incorporation decreased with increase in temperature above 45 degrees C. Initially, oleic acid incorporation increased with increase in substrate molar ratio up to 1:3. LIP1 was also compared with Lipozyme RM IM as biocatalysts. The tested reaction parameters were selected on the basis of maximum incorporation of C18:1 obtained during optimization of LIP1 reaction conditions. Reaction temperature was maintained at 45, 55, and 65 degrees C. Lipozyme RM IM gave highest oleic acid incorporation (49.4%) at 65 degrees C with methyl oleate as acyl donor. Statistically significant (P < 0.05) differences were observed for both enzymes. SL prepared using Lipozyme RM IM may be more suitable for possible use in human milk fat substitutes.

SPPS of protected peptidyl aminoalkyl amides.

PubMed

Karavoltsos, Manolis; Mourtas, Spyros; Gatos, Dimitrios; Barlos, Kleomenis

2002-11-01

Monophthaloyl diamines derived from naturally occurring amino acids were attached through their free amino functions to resins of the trityl type. The phthaloyl groups were removed by hydrazinolysis, and peptide chains were assembled using Fmoc/tBu-amino acids on the liberated amino functions. The peptidyl aminoalkyl amides obtained were cleaved from the resins by mild acidolysis, with the tBu-side chain protection remaining intact.

Benzoylureas as removable cis amide inducers: synthesis of cyclic amides via ring closing metathesis (RCM).

PubMed

Brady, Ryan M; Khakham, Yelena; Lessene, Guillaume; Baell, Jonathan B

2011-02-07

Rapid and high yielding synthesis of medium ring lactams was made possible through the use of a benzoylurea auxiliary that serves to stabilize a cisoid amide conformation, facilitating cyclization. The auxiliary is released after activation under the mild conditions required to deprotect a primary amine, such as acidolysis of a Boc group in the examples given here. This methodology is a promising tool for the synthesis of medium ring lactams, macrocyclic natural products and peptides.

Synthesis of nano-TiO2 photocatalysts with tunable Fe doping concentration from Ti-bearing tailings

NASA Astrophysics Data System (ADS)

Sui, Yulei; Liu, Qingxia; Jiang, Tao; Guo, Yufeng

2018-01-01

In this work, highly pure nano-TiO2 photocatalysts with varying Fe doping concentration were successfully synthesized from low-cost Ti-bearing tailings by an acidolysis-hydrothermal route. The effects of H2SO4 concentration, leaching temperature, acid/tailings ratio and leaching time on the recovery of TiO2 from the tailings were investigated. Synthesized samples were characterized by XRD, TEM, EDS, XPS, and UV-vis spectroscopy. The results showed that the material prepared is characteristic anatase with the average size of 20 nm and the Fe doping concentration in the synthesized nano-TiO2 is tunable. The photocatalytic activity of synthesized nano-TiO2 photocatalyst was also evaluated by the photodegradation of Rhodamine B under visible light and UV light irradiation. Our study demonstrates a low-cost approach to synthesize highly efficient and visible light responsive catalysts.

Synthesis of structured triacylglycerols enriched in n-3 fatty acids by immobilized microbial lipase.

PubMed

Araújo, Maria Elisa Melo Branco de; Campos, Paula Renata Bueno; Alberto, Thiago Grando; Contesini, Fabiano Jares; Carvalho, Patrícia de Oliveira

The search for new biocatalysts has aroused great interest due to the variety of micro-organisms and their role as enzyme producers. Native lipases from Aspergillus niger and Rhizopus javanicus were used to enrich the n-3 long-chain polyunsaturated fatty acids content in the triacylglycerols of soybean oil by acidolysis with free fatty acids from sardine oil in solvent-free media. For the immobilization process, the best lipase/support ratios were 1:3 (w/w) for Aspergillus niger lipase and 1:5 (w/w) for Rhizopus javanicus lipase using Amberlite MB-1. Both lipases maintained constant activity for 6 months at 4°C. Reaction time, sardine-free fatty acids:soybean oil mole ratio and initial water content of the lipase were investigated to determine their effects on n-3 long-chain polyunsaturated fatty acids incorporation into soybean oil. Structured triacylglycerols with 11.7 and 7.2% of eicosapentaenoic acid+docosahexaenoic acid were obtained using Aspergillus niger lipase and Rhizopus javanicus lipase, decreasing the n-6/n-3 fatty acids ratio of soybean oil (11:1 to 3.5:1 and 4.7:1, respectively). The best reaction conditions were: initial water content of lipase of 0.86% (w/w), sardine-free faty acids:soybean oil mole ratio of 3:1 and reaction time of 36h, at 40°C. The significant factors for the acidolysis reaction were the sardine-free fatty acids:soybean oil mole ratio and reaction time. The characterization of structured triacylglycerols was obtained using easy ambient sonic-spray ionization mass spectrometry. The enzymatic reaction led to the formation of many structured triacylglycerols containing eicosapentaenoic acid, docosahexaenoic acid or both polyunsaturated fatty acids. Copyright © 2016 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

Effects of dietary oxidized konjac glucomannan sulfates (OKGMS) and acidolysis-oxidized konjac glucomannan (A-OKGM) on the immunity and expression of immune-related genes of Schizothorax prenanti.

PubMed

Chen, Mingrui; Wang, Hongjie; Yan, Qiuping; Zheng, Qiaoran; Yang, Min; Lv, Zhenzhen; He, Mei; Feng, Limei; Zhao, Jiaqi; Tang, Tingting; Wu, Yinglong

2016-09-01

In the present study, konjac glucomannan (KGM) was degraded by H2O2, and then used trisulfonated sodium amine and HCl, individually, to obtain two kinds of derivatives: oxidized konjac glucomannan sulfates (OKGMS) and acidolysis-oxidized konjac glucomannan (A-OKGM). The effects of two OKGM modified products on the immune parameters and expressions of toll-like receptor 22 (TLR22), myeloid differentiation factor 88 (MyD88) and interferon regulatory factors 7 (IRF7) genes in Schizothorax prenanti were determined. The alternative haemolytic complement (ACH50) activity was found to be significantly increased by the OKGMS diets. The immunoglobulin M (IgM) level was significantly enhanced by the OKGMS diets. The lysozyme activity was significantly increased by both OKGMS and A-OKGM diets. The superoxide dismutase (T-SOD) activity in fish fed with all doses of OKGMS diets was significantly higher than that in fish fed with basal diet. The glutathione peroxidase (GSH-PX) activity in fish fed with 0.8% and 1.6% A-OKGM diets was significantly higher than control group. The malondialdehyde (MDA) level was significantly decreased by both OKGMS and A-OKGM diets. The 0.8% A-OKGM diet significantly up-regulated TLR22 gene expression in the head kidney and spleen. TLR22 gene expression was significantly promoted by all OKGMS diets in the mesonephros and liver. The MyD88 mRNA level in 1.6% A-OKGM group significantly increased in the head kidney. The low dose of OKGMS significantly induced the MyD88 gene expression in the mesonephros, gut and liver, while 0.8% A-OKGM group also showed a significantly enhanced MyD88 mRNA expression in the gut. High dose of OKGMS significantly increased the IRF7 mRNA expression in the mesonephros and spleen. Fish fed with low dose of A-OKGM showed significantly higher expression of IRF7 in the gut and liver. Present study suggested that OKGMS and A-OKGM can act as immunostimulant to improve the immune indexes and up-regulate the immune-related gene expressions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Facile preparation of magnetic carbon nanotubes-immobilized lipase for highly efficient synthesis of 1,3-dioleoyl-2-palmitoylglycerol-rich human milk fat substitutes.

PubMed

Zheng, Mingming; Wang, Shi; Xiang, Xia; Shi, Jie; Huang, Juan; Deng, Qianchun; Huang, Fenghong; Xiao, Junyong

2017-08-01

In this study, Candida lipolytica lipase (CLL) was immobilized on magnetic multi-walled carbon nanotubes (mMWCNTs) via hydrophobic and cation-exchange interaction. The resultant immobilized CLL showed much better thermal stability, biocatalyst activity and easier recycling than the free form. A method for efficient enzymatic acidolysis of tripalmitin (PPP) with oleic acid (OA), to produce OPO-rich TAGs, was developed, using the immobilized CLL as the biocatalyst. Under optimized conditions (2% water, 20mg/ml enzyme, 1:6 PPP/OA, 50°C, 2h), the content of OPO in the final product reached 46.5%. CLL@mMWCNTs had a better activity and manipulative stability than commercial lipases. More importantly, the feasibility of CLL@mMWCNTs was also validated in the practical production of OPO-rich TAGs, using lard and restructured palm oil as the raw material. These results suggest that CLL@mMWCNTs is a promising biocatalyst for the OPO-rich TAGs production and will be helpful for the infant formula industry. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simple and Fast Extraction-Coupled UPLC-MS/MS Method for the Determination of Mequindox and Its Major Metabolites in Food Animal Tissues.

PubMed

You, Yanli; Song, Liting; Li, Yanshen; Wu, Yongtao; Xin, Mao

2016-03-23

This research described a sensitive and rapid UPLC-MS/MS method for the determination of mequindox and its six major metabolites in chicken muscle, chicken liver, swine muscle, and swine liver. Among the metabolites, carbonyl reduction-1,4-bisdesoxy-mequindox is novel. Target analytes could be extracted by ethyl acetate without any acidolysis or enzymolysis steps. After purification by a Bond Elut C18 cartridge, analysis was carried out by UPLC-MS/MS using positive ion multiple reaction monitoring (MRM) mode. Validation was performed in spiked samples, and mean recoveries ranged from 64.3 to 114.4%, with intraday and interday variations of less than 14.7 and 19.2%, respectively. The limit of detection (LOD) was <1.0 μg kg(-1), whereas the limit of quantification (LOQ) was <4.0 μg kg(-1). This procedure will help monitor mequindox residues in animal-derived food, and it will also facilitate further pharmacokinetics of mequindox.

Study of Silicidation Process of Tungsten Catalyzer during Silicon Film Deposition in Catalytic Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Honda, Kazuhiro; Ohdaira, Keisuke; Matsumura, Hideki

2008-05-01

In catalytic chemical vapor deposition (Cat-CVD), often called hot-wire CVD, source gases are decomposed by catalytic cracking reactions with heated catalyzing metal wires. In the case of silicon (Si) film deposition, such metal wires are often converted to silicide, which shortens the lifetime of catalyzing wires. As a catalyzer, tungsten (W) is widely used. Thus, the process of silicidation of a W catalyzer at temperatures over 1650 °C, which is the temperature used in Cat-CVD for Si film deposition, was studied extensively in various experiments. It is found that two phases of tungsten-silicide, WSi2 and W5Si3, are formed at this temperature, and that the radiation emissivity of WSi2 is 1.2 to 1.7 times higher than that of W5Si3 and pure W. The increase of surface emissivity due to the formation of WSi2 decreases the catalyzer surface temperature which induces further growth of the tungsten-silicide layer. It is also found that the suppression of WSi2 formation by elevating catalyzer temperatures over 1750 °C is a key to extending the lifetime of the W catalyzer in Cat-CVD.

Surface-catalyzed air oxidation of hydrazines: Environmental chamber studies

NASA Technical Reports Server (NTRS)

Kilduff, Jan E.; Davis, Dennis D.; Koontz, Steven L.

1988-01-01

The surface-catalyzed air oxidation reactions of fuel hydrazines were studied in a 6500-liter fluorocarbon-film chamber at 80 to 100 ppm concentrations. First-order rate constants for the reactions catalyzed by aluminum, water-damaged aluminum (Al/Al2O3), stainless steel 304L, galvanized steel and titanium plates with surface areas of 2 to 24 sq m were determined. With 23.8 sq m of Al/Al2O3 the surface-catalyzed air oxidation of hydrazine had a half-life of 2 hours, diimide (N2H2) was observed as an intermediate and traces of ammonia were present in the final product mixture. The Al/Al2O3 catalyzed oxidation of monomethylhydrazine yielded methyldiazine (HN = NCH3) as an intermediate and traces of methanol. Unsymmetrical dimethylhydrazine gave no detectable products. The relative reactivities of hydrazine, MMH and UDMH were 130 : 7.3 : 1.0, respectively. The rate constants for Al/Al2O3-catalyzed oxidation of hydrazine and MMH were proportional to the square of the surface area of the plates. Mechanisms for the surface-catalyzed oxidation of hydrazine and diimide and the formation of ammonia are proposed.

Rh-Catalyzed Annulations of N-Methoxybenzamides and Ketenimines: Sterically and Electronically Controlled Synthesis of Isoquinolinones and Isoindolinones.

PubMed

Zhou, Xiaorong; Zhang, Zhiyin; Zhao, Hongyang; Lu, Ping; Wang, Yanguang

2017-04-07

Rhodium-catalyzed C-H activation/annulation reactions of ketenimines with N-methoxybenzamides are reported. The outcome of reactions is dependent on the structure of ketenimines. The β-alkyl-substituted ketenimines furnish 3-iminoisoquinolin-1(2H)-ones in a formal [4 + 2] annulation manner, while the β-ester substituted ketenimines afford 3-aminoisoindolin-1-ones in a formal [4 + 1] annulation manner. The synthesized [4 + 2] products undergo an intramolecular Cu-catalyzed C-N coupling to be converted to benzo[4,5]imidazo[1,2-b]isoquinolin-11-ones, which can be directly prepared from ketenimines and N-methoxybenzamides by a one-pot Rh-catalyzed annulation/Cu-catalyzed C-N coupling sequence.

Resting State and Elementary Steps of the Coupling of Aryl Halides with Thiols Catalyzed by Alkylbisphosphine Complexes of Palladium

PubMed Central

Alvaro, Elsa

2010-01-01

Detailed mechanistic studies on the coupling of aryl halides with thiols catalyzed by palladium complexes of the alkylbisphosphine ligand CyPF-tBu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylferrocene) are reported. The elementary steps that constitute the catalytic cycle, i.e. oxidative addition, transmetalation and reductive elimination, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF-tBu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)2 and CyPF-tBu, a combination of Pd(dba)2 and CyPF-tBu, or the likely intermediate Pd(CyPF-tBu)(Ar)(Br). These show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc)2 and CyPF-tBu was the palladium bis-thiolate complex [Pd(CyPF-tBu)(SR)2] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd2(dba)3 and CyPF-tBu was the binuclear complex [Pd(CyPF-tBu)]2(μ2, η2-dba) (9). The resting state of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF-tBu)(p-tolyl)(Br)] (3a) was the hydridopalladium thiolate complex [Pd(CyPF-tBu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF-tBu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc)2 or Pd(dba)2. Our data indicate that the resting states of these reactions are similar to each other and that our mechanistic conclusions about reactions catalyzed by palladium and CyPF-tBu can be extrapolated to reactions catalyzed by complexes of other electron-rich bisphosphines. PMID:19453106

Functional diversity of 2-oxoglutarate/Fe(II)-dependent dioxygenases in plant metabolism

PubMed Central

Farrow, Scott C.; Facchini, Peter J.

2014-01-01

Oxidative enzymes catalyze many different reactions in plant metabolism. Among this suite of enzymes are the 2-oxoglutarate/Fe(II)-dependent dioxygenases (2-ODDs). Cytochromes P450 (CYPs) as often considered the most versatile oxidative enzymes in nature, but the diversity and complexity of reactions catalyzed by 2-ODDs is superior to the CYPs. The list of oxidative reactions catalyzed by 2-ODDs includes hydroxylations, demethylations, desaturations, ring closure, ring cleavage, epimerization, rearrangement, halogenation, and demethylenation. Furthermore, recent work, including the discovery of 2-ODDs involved in epigenetic regulation, and others catalyzing several characteristic steps in specialized metabolic pathways, support the argument that 2-ODDs are among the most versatile and important oxidizing biological catalysts. In this review, we survey and summarize the pertinent literature with a focus on several key reactions catalyzed by 2-ODDs, and discuss the significance and impact of these enzymes in plant metabolism. PMID:25346740

Removal of emerging pollutants by Ru/TiO2-catalyzed permanganate oxidation.

PubMed

Zhang, Jing; Sun, Bo; Xiong, Xinmei; Gao, Naiyun; Song, Weihua; Du, Erdeng; Guan, Xiaohong; Zhou, Gongming

2014-10-15

TiO2 supported ruthenium nanoparticles, Ru/TiO2 (0.94‰ as Ru), was synthesized to catalyze permanganate oxidation for degrading emerging pollutants (EPs) with diverse organic moieties. The presence of 1.0 g L(-1) Ru/TiO2 increased the second order reaction rate constants of bisphenol A, diclofenac, acetaminophen, sulfamethoxazole, benzotriazole, carbamazepine, butylparaben, diclofenac, ciprofloxacin and aniline at mg L(-1) level (5.0 μM) by permanganate oxidation at pH 7.0 by 0.3-119 times. The second order reaction rate constants of EPs with permanganate or Ru/TiO2-catalyzed permanganate oxidation obtained at EPs concentration of mg L(-1) level (5.0 μM) underestimated those obtained at EPs concentration of μg L(-1) level (0.050 μM). Ru/TiO2-catalyzed permanganate could decompose a mixture of nine EPs at μg L(-1) level efficiently and the second order rate constant for each EP was not decreased due to the competition of other EPs. The toxicity tests revealed that Ru/TiO2-catalyzed permanganate oxidation was effective not only for elimination of EPs but also for detoxification. The removal rates of sulfamethoxazole by Ru/TiO2-catalyzed permanganate oxidation in ten successive cycles remained almost constant in ultrapure water and slightly decreased in Songhua river water since the sixth run, indicating the satisfactory stability of Ru/TiO2. Ru/TiO2-catalyzed permanganate oxidation was selective and could remove selected EPs spiked in real waters more efficiently than chlorination. Therefore, Ru/TiO2-catalyzed permanganate oxidation is promising for removing EPs with electron-rich moieties. Copyright © 2014 Elsevier Ltd. All rights reserved.

Scale-up and process integration of sugar production by acidolysis of municipal solid waste/corn stover blends in ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Chenlin; Liang, Ling; Sun, Ning

The study presents the successful scale-up demonstration of the acid-assisted IL deconstruction on feedstock blends of municipal solid wastes and agricultural residues (corn stover) by 30-fold, relative to the bench scale (6L vs 0.2L), at 10% solid loading. By integrating IL pretreatment and acid hydrolysis with subsequent centrifugation and extraction, the sugar and lignin products can be further recovered efficiently. This scale-up development at Advanced Biofuels/Bioproducts Process Demonstration Unit (ABPDU) will leverage the opportunity and synergistic efforts towards developing a cost-effective IL based deconstruction technology by drastically eliminating enzyme, reducing water usage, and simplifying the downstream sugar/lignin recovery and ILmore » recycling. Results indicate that MSW blends are viable and valuable resource to consider when assessing biomass availability and affordability for lignocellulosic biorefineries. This scale-up evaluation demonstrates that the acid-assisted IL deconstruction technology can be effectively scaled up to larger operations and the current study established the baseline of scaling parameters for this process.« less

Scale-up and process integration of sugar production by acidolysis of municipal solid waste/corn stover blends in ionic liquids

DOE PAGES

Li, Chenlin; Liang, Ling; Sun, Ning; ...

2017-01-05

The study presents the successful scale-up demonstration of the acid-assisted IL deconstruction on feedstock blends of municipal solid wastes and agricultural residues (corn stover) by 30-fold, relative to the bench scale (6L vs 0.2L), at 10% solid loading. By integrating IL pretreatment and acid hydrolysis with subsequent centrifugation and extraction, the sugar and lignin products can be further recovered efficiently. This scale-up development at Advanced Biofuels/Bioproducts Process Demonstration Unit (ABPDU) will leverage the opportunity and synergistic efforts towards developing a cost-effective IL based deconstruction technology by drastically eliminating enzyme, reducing water usage, and simplifying the downstream sugar/lignin recovery and ILmore » recycling. Results indicate that MSW blends are viable and valuable resource to consider when assessing biomass availability and affordability for lignocellulosic biorefineries. This scale-up evaluation demonstrates that the acid-assisted IL deconstruction technology can be effectively scaled up to larger operations and the current study established the baseline of scaling parameters for this process.« less

Synthesis of 1-methyleneindenes via palladium-catalyzed tandem reactions.

PubMed

Ye, Shengqing; Gao, Ke; Zhou, Haibo; Yang, Xiaodi; Wu, Jie

2009-09-28

Palladium-catalyzed tandem reactions of 2-alkenylphenyl-acetylenes with CuCl2 or CuBr2 afforded 3-chloro- or 3-bromo-1-methyleneindenes in good yields; these compounds could be further elaborated via palladium-catalyzed coupling reactions.

Mechanistic Comparison Between Pd-Catalyzed Ligand Directed C-H Chlorination and C-H Acetoxylation

PubMed Central

Stowers, Kara J.; Sanford, Melanie S.

2009-01-01

This communication describes detailed investigations of the mechanism of the Pd-catalyzed C-H chlorination and acetoxylation of 2-ortho-tolylpyridine. Under the conditions examined, both reactions proceed via rate limiting cyclopalladation. However, substrate and catalyst order as well as Hammett data indicate that the intimate mechanism of cyclopalladation differs significantly between PdCl2-catalyzed chlorination and Pd(OAc)2-catalyzed acetoxylation. PMID:19754074

Cu2+ -Modified Metal-Organic Framework Nanoparticles: A Peroxidase-Mimicking Nanoenzyme.

PubMed

Chen, Wei-Hai; Vázquez-González, Margarita; Kozell, Anna; Cecconello, Alessandro; Willner, Itamar

2018-02-01

The synthesis and characterization of UiO-type metal-organic framework nanoparticles (NMOFs) composed of Zr 4+ ions bridged by 2,2'-bipyridine-5,5'-dicarboxylic acid ligands and the postmodification of the NMOFs with Cu 2+ ions are described. The resulting Cu 2+ -modified NMOFs, Cu 2+ -NMOFs, exhibit peroxidase-like catalytic activities reflected by the catalyzed oxidation of Amplex-Red to the fluorescent Resorufin by H 2 O 2 , the catalyzed oxidation of dopamine to aminochrome by H 2 O 2 , and the catalyzed generation of chemiluminescence in the presence of luminol/H 2 O 2 . Also, the Cu 2+ -NMOFs mimic NADH peroxidase functions and catalyze the oxidation of dihydronicotinamide adenine dinucleotide, NADH, to nicotinamide adenine dinucleotide, NAD + , in the presence of H 2 O 2 . The Cu 2+ -NMOFs-catalyzed generation of chemiluminescence in the presence of luminol/H 2 O 2 is used to develop a glucose sensor by monitoring the H 2 O 2 formed by the aerobic oxidation of glucose to gluconic acid in the presence of glucose oxidase. Furthermore, loading the Cu 2+ -NMOFs with fluorescein and activating the catalyzed generation of chemiluminescence in the presence of luminol/H 2 O 2 yield an efficient chemiluminescence resonance energy transfer (CRET) process to the fluorescein reflected by the activation of the fluorescence of the dye (λ = 520 nm, CRET efficiency 35%). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-dependent reactions for the synthesis of β-keto-benzo-δ-sultone scaffolds via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences.

PubMed

Ghandi, Mehdi; Bozcheloei, Abolfazl Hasani; Nazari, Seyed Hadi; Sadeghzadeh, Masoud

2011-12-16

We have developed a solvent-dependent method for the synthesis of novel benzo-δ-sultone scaffolds. A variety of benzylbenzo[e][1,2]oxathiin-4(3H)-one-2,2-dioxides were obtained in high yields in DMF using a one-pot, DBU-catalyzed condensation of 2-hydroxybenzaldehydes with a number of (E)-2-phenylethenesulfonyl chlorides. On the other hand, the initially prepared 2-formylphenyl-(E)-2-phenylethenesulfonate derivatives underwent DBU-catalyzed reactions to a series of 3-[methoxy(phenyl)methyl]benzo[e][1,2]oxathiine-2,2-dioxides in moderate to good yields in MeOH. These reactions presumably proceed via DBU-catalyzed O-sulfonylation/intramolecular Baylis-Hillman/1,3-H shift or dehydration tandem sequences, respectively.

Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

PubMed

Zhang, Pan; Ni, Shao-Fei; Dang, Li

2016-09-20

The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative evaluation of three lignin isolation protocols for various wood species.

PubMed

Guerra, Anderson; Filpponen, Ilari; Lucia, Lucian A; Argyropoulos, Dimitris S

2006-12-27

Milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL) were isolated from different wood species and characterized by various techniques. The EMAL protocol offered gravimetric lignin yields 2-5 times greater than those of the corresponding MWL and CEL. The purities of the EMALs were 3.75-10.6% higher than those of their corresponding CELs, depending upon the wood species from which they were isolated. Molecular weight analyses showed that the EMAL protocol isolates lignin fractions that are not accessed by the other procedures evaluated, while 31P NMR spectroscopy revealed that MWL is more condensed and bears more phenolic hydroxyl groups than EMAL and CEL. The yields and purities of EMAL, MWL, and CEL from hardwood were greater than those obtained for the examined softwoods. Structural details obtained by DFRC (derivatization followed by reductive cleavage)/31P NMR revealed different contents of condensed and uncondensed beta-O-aryl ether structures, dibenzodioxocins, and condensed and uncondensed phenolic hydroxyl and carboxylic acid groups within lignins isolated from different wood species.

Impact of steam explosion on the wheat straw lignin structure studied by solution-state nuclear magnetic resonance and density functional methods.

PubMed

Heikkinen, Harri; Elder, Thomas; Maaheimo, Hannu; Rovio, Stella; Rahikainen, Jenni; Kruus, Kristiina; Tamminen, Tarja

2014-10-29

Chemical changes of lignin induced by the steam explosion (SE) process were elucidated. Wheat straw was studied as the raw material, and lignins were isolated by the enzymatic mild acidolysis lignin (EMAL) procedure before and after the SE treatment for analyses mainly by two-dimensional (2D) [heteronuclear single-quantum coherence (HSQC) and heteronuclear multiple-bond correlation (HMBC)] and (31)P nuclear magnetic resonance (NMR). The β-O-4 structures were found to be homolytically cleaved, followed by recoupling to β-5 linkages. The homolytic cleavage/recoupling reactions were also studied by computational methods, which verified their thermodynamic feasibility. The presence of the tricin bound to wheat straw lignin was confirmed, and it was shown to participate in lignin reactions during the SE treatment. The preferred homolytic β-O-4 cleavage reaction was calculated to follow bond dissociation energies: G-O-G (guaiacyl) (69.7 kcal/mol) > G-O-S (syringyl) (68.4 kcal/mol) > G-O-T (tricin) (67.0 kcal/mol).

Water Oxidation by a Cytochrome P450: Mechanism and Function of the Reaction

PubMed Central

Prasad, Brinda; Mah, Derrick J.; Lewis, Andrew R.; Plettner, Erika

2013-01-01

P450cam (CYP101A1) is a bacterial monooxygenase that is known to catalyze the oxidation of camphor, the first committed step in camphor degradation, with simultaneous reduction of oxygen (O2). We report that P450cam catalysis is controlled by oxygen levels: at high O2 concentration, P450cam catalyzes the known oxidation reaction, whereas at low O2 concentration the enzyme catalyzes the reduction of camphor to borneol. We confirmed, using 17O and 2H NMR, that the hydrogen atom added to camphor comes from water, which is oxidized to hydrogen peroxide (H2O2). This is the first time a cytochrome P450 has been observed to catalyze oxidation of water to H2O2, a difficult reaction to catalyze due to its high barrier. The reduction of camphor and simultaneous oxidation of water are likely catalyzed by the iron-oxo intermediate of P450cam, and we present a plausible mechanism that accounts for the 1∶1 borneol:H2O2 stoichiometry we observed. This reaction has an adaptive value to bacteria that express this camphor catabolism pathway, which requires O2, for two reasons: 1) the borneol and H2O2 mixture generated is toxic to other bacteria and 2) borneol down-regulates the expression of P450cam and its electron transfer partners. Since the reaction described here only occurs under low O2 conditions, the down-regulation only occurs when O2 is scarce. PMID:23634216

Copper-catalyzed synthesis of phenanthridine derivatives under an oxygen atmosphere starting from biaryl-2-carbonitriles and Grignard reagents.

PubMed

Zhang, Line; Ang, Gim Yean; Chiba, Shunsuke

2010-08-20

A copper-catalyzed synthesis of phenanthridine derivatives was developed starting from biaryl-2-carbonitriles and Grignard reagents. The present transformation is carried out by a sequence of nucleophilic addition of Grignard reagents to biaryl-2-carbonitriles to form N-H imines and their Cu-catalyzed C-N bond formation on the aromatic C-H bond, where molecular oxygen is a prerequisite to achieve the catalytic process.

Muon Catalyzed Fusion

NASA Technical Reports Server (NTRS)

Armour, Edward A.G.

2007-01-01

Muon catalyzed fusion is a process in which a negatively charged muon combines with two nuclei of isotopes of hydrogen, e.g, a proton and a deuteron or a deuteron and a triton, to form a muonic molecular ion in which the binding is so tight that nuclear fusion occurs. The muon is normally released after fusion has taken place and so can catalyze further fusions. As the muon has a mean lifetime of 2.2 microseconds, this is the maximum period over which a muon can participate in this process. This article gives an outline of the history of muon catalyzed fusion from 1947, when it was first realised that such a process might occur, to the present day. It includes a description of the contribution that Drachrnan has made to the theory of muon catalyzed fusion and the influence this has had on the author's research.

Enzymatic synthesis of capric acid-rich structured lipids (MUM type) using Candida antarctica lipase.

PubMed

SilRoy, Sumita; Ghosh, Mahua

2011-01-01

The objective of the work was to produce capric acid rich structured lipids starting from various Indian indigenous vegetable oils, such as rice bran, ground nut and mustard oils. Acidolysis reaction between individual vegetable oils and capric acid in one is to three molar ratios at 45 degree centigrade temperature was carried out using position specific Candida antarctica lipase so as to protect the Sn-2 position of the oils which are rich in unsaturated fatty acids. The incorporation of capric acid depended on the reaction time showing 6 % within 6 h and 30.8 % in 72 h with rice bran oil. Similarly, in ground nut oil incorporation of capric acid was 34.2 % in 72 h compared to 5.3 % in 6 h. Thus mustard oil showed much lower incorporation than the other two oils, with 3.3 % and 19.5 % in 6 and 72 h respectively. The incorporation of capric acid was influenced by the nature of the fatty acids present in the original oil. The fatty acid composition of Sn-2 position of the structured triacylglycerols of the three oils revealed that capric acid was mainly replacing the fatty acids occupying the Sn-1 and 3 positions of the triglyceride molecule.

The mechanism of transition-metal (Cu or Pd)-catalyzed synthesis of benzimidazoles from amidines: theoretical investigation.

PubMed

Li, Juan; Gu, Honghong; Wu, Caihong; Du, Lijuan

2014-11-28

In this study, the Cu(OAc)2- and [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines were theoretically investigated using density functional theory calculations. For the Cu-catalyzed system, our calculations supported a four-step-pathway involving C-H activation of an arene with Cu(II) via concerted metalation-deprotonation (CMD), followed by oxidation of the Cu(II) intermediate and deprotonation of the imino group by Cu(III), and finally reductive elimination from Cu(III). In our calculations, the barriers for the CMD step and the oxidation step are the same. The results are different from the ones reported by Fu et al. in which the whole reaction mechanism includes three steps and the CMD step is rate determining. On the basis of the calculation results for the [PdCl2(PhCN)2]-catalyzed system, C-H bond breaking by CMD occurs first, followed by the rate-determining C-N bond formation and N-H deprotonation. Pd(III) species is not involved in the [PdCl2(PhCN)2]-catalyzed syntheses of benzimidazoles from amidines.

Dual chemistry catalyzed by human acireductone dioxygenase

PubMed Central

Deshpande, Aditi R.; Pochapsky, Thomas C.; Petsko, Gregory A.

2017-01-01

Abstract Acireductone dioxygenase (ARD) from the methionine salvage pathway of Klebsiella oxytoca is the only known naturally occurring metalloenzyme that catalyzes different reactions in vivo based solely on the identity of the divalent transition metal ion (Fe2+ or Ni2+) bound in the active site. The iron-containing isozyme catalyzes the cleavage of substrate 1,2-dihydroxy-3-keto-5-(thiomethyl)pent-1-ene (acireductone) by O2 to formate and the ketoacid precursor of methionine, whereas the nickel-containing isozyme uses the same substrates to catalyze an off-pathway shunt to form methylthiopropionate, carbon monoxide and formate. This dual chemistry was recently demonstrated in vitro by ARD from Mus musculus (MmARD), providing the first example of a mammalian ARD exhibiting metal-dependent catalysis. We now show that human ARD (HsARD) is also capable of metal-dependent dual chemistry. Recombinant HsARD was expressed and purified to obtain a homogeneous enzyme with a single transition metal ion bound. As with MmARD, the Fe2+-bound HsARD shows the highest activity and catalyzes on-pathway chemistry, whereas Ni2+, Co2+ or Mn2+ forms catalyze off-pathway chemistry. The thermal stability of the HsARD isozymes is a function of the metal ion identity, with Ni2+-bound HsARD being the most stable followed by Co2+ and Fe2+, and Mn2+-bound HsARD being the least stable. As with the bacterial ARD, solution NMR data suggest that HsARD isozymes can have significant structural differences depending upon the metal ion bound. PMID:28062648

A novel on-line gold nanoparticle-catalyzed luminol chemiluminescence detector for high-performance liquid chromatography.

PubMed

Zhang, Qun Lin; Wu, Liang; Lv, Chen; Zhang, Xiao Yue

2012-06-15

A novel on-line gold nanoparticle-catalyzed luminol-H(2)O(2) chemiluminescence (CL) detector for high-performance liquid chromatography (HPLC) was established, in which gold nanoparticles were produced by the on-line reaction of H(2)O(2), NaHCO(3)-Na(2)CO(3) (buffer solution of luminol), and HAuCl(4). Eight phenolic compounds (gallic acid, protocatechuic acid, protocatechuic aldehyde, 2,5-dihydroxybenzoic acid, caffeic acid, 2,3-dihydroxybenzoic acid, (+)-catechin, and (-)-epicatechin) were chosen as the model compounds. Every separated phenolic compound in the column eluent strongly enhanced the CL signal of on-line gold nanoparticle-catalyzed luminol system. The CL and UV-visible absorption spectra and transmission electron microscopy studies were carried out, and the CL enhancement mechanism was ascribed to that the presence of phenolic compound promoted the on-line formation of 38-nm-diameter gold nanoparticles, which better catalyzed the luminol-H(2)O(2) CL reaction. The effects of methanol and phosphoric acid in the proposed HPLC configuration were performed by two gradient elution programs, and the baseline profile revealed that on-line gold nanoparticle-catalyzed luminol-H(2)O(2) CL detector had better compatibility than 38 nm gold colloids-luminol-H(2)O(2) CL detector. The proposed CL detector exhibits excellent analytical performance with the low detection limit (S/N=3) of 0.53-0.97 ng/mL (10.6-19.4 pg) phenolic compounds, and offers a new strategy for developing on-line nanoparticle-catalyzed CL detector for HPLC with sensitive analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Synthesis of δ- and α-Carbolines via Nickel-Catalyzed [2 + 2 + 2] Cycloaddition of Functionalized Alkyne-Nitriles with Alkynes.

PubMed

Wang, Gaonan; You, Xu; Gan, Yi; Liu, Yuanhong

2017-01-06

A new method for the synthesis of δ- and α-carbolines through Ni-catalyzed [2 + 2 + 2] cycloaddition of ynamide-nitriles or alkyne-cyanamides with alkynes has been developed. The catalytic system of NiCl 2 (DME)/dppp/Zn with a low-cost Ni(II)-precursor was first utilized in Ni-catalyzed [2 + 2 + 2] cycloaddition reactions, and the in situ generated Lewis acid may play an important role for the successful transformation. Not only internal alkynes but also terminal alkynes undergo the desired cycloaddition reactions efficiently to furnish the carboline derivatives with wide diversity and functional group tolerance.

A facile synthesis of pyrrolo[2,3-b]quinolines via a Rh(I)-catalyzed carbodiimide-Pauson-Khand-type reaction.

PubMed

Saito, Takao; Furukawa, Naoki; Otani, Takashi

2010-03-07

A new straightforward synthetic method for 2,3-dihydro-1H-pyrrolo[2,3-b]quinolin-2-ones via a [RhCl(CO)(2)](2)-dppp catalyzed Pauson-Khand-type reaction of N-[2-(2-alkyn-1-yl)phenyl]carbodiimides is reported.

Enantioselective synthesis of C2 -symmetric spirobipyridine ligands through cationic Rh(I)/modified-BINAP- catalyzed double [2 + 2 + 2] cycloaddition.

PubMed

Wada, Azusa; Noguchi, Keiichi; Hirano, Masao; Tanaka, Ken

2007-03-29

[structure: see text]. Enantioenriched C2-symmetric spirobipyridine ligands were efficiently synthesized through a cationic rhodium(I)/(R)-Segphos or (R)-H8-BINAP complex-catalyzed enantioselective intramolecular double [2 + 2 + 2] cycloaddition of bis-diynenitriles.

GENERAL: Kinetic Behaviors of Catalysis-Driven Growth of Three-Species Aggregates on Base of Exchange-Driven Aggregations

NASA Astrophysics Data System (ADS)

Sun, Yun-Fei; Chen, Dan; Lin, Zhen-Quan; Ke, Jian-Hong

2009-06-01

We propose a solvable aggregation model to mimic the evolution of population A, asset B, and the quantifiable resource C in a society. In this system, the population and asset aggregates themselves grow through self-exchanges with the rate kernels K1(k, j) = K1kj and K2(k, j) = K2kj, respectively. The actions of the population and asset aggregations on the aggregation evolution of resource aggregates are described by the population-catalyzed monomer death of resource aggregates and asset-catalyzed monomer birth of resource aggregates with the rate kernels J1(k, j) = J1k and J2(k, j) = J2k, respectively. Meanwhile, the asset and resource aggregates conjunctly catalyze the monomer birth of population aggregates with the rate kernel I1(k, i, j) = I1kiμjη, and population and resource aggregates conjunctly catalyze the monomer birth of asset aggregates with the rate kernel I2(k, i, j) = I2kivjη. The kinetic behaviors of species A, B, and C are investigated by means of the mean-field rate equation approach. The effects of the population-catalyzed death and asset-catalyzed birth on the evolution of resource aggregates based on the self-exchanges of population and asset appear in effective forms. The coefficients of the effective population-catalyzed death and the asset-catalyzed birth are expressed as J1e = J1/K1 and J2e = J2/K2, respectively. The aggregate size distribution of C species is found to be crucially dominated by the competition between the effective death and the effective birth. It satisfies the conventional scaling form, generalized scaling form, and modified scaling form in the cases of J1e < J2e, J1e = J2e, and J1e > J2e, respectively. Meanwhile, we also find the aggregate size distributions of populations and assets both fall into two distinct categories for different parameters μ, ν, and η: (i) When μ = ν = η = 0 and μ = ν = 0, η = 1, the population and asset aggregates obey the generalized scaling forms; and (ii) When μ = ν = 1, η = 0, and μ = ν = η = 1, the population and asset aggregates experience gelation transitions at finite times and the scaling forms break down.

New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Qinhua

2004-12-19

The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I 2, ICl, PhSeCl, PhSCl and p-O 2NC 6H 4SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellentmore » yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution. A relatively efficient synthesis of cyclopropanes has been developed using palladium-catalyzed C-H activation chemistry, in which two new carbon-carbon bonds are formed in a single step. This method involves the palladium-catalyzed activation of relatively unreactive C-H bonds, and provides a very efficient way to synthesize cyclopropapyrrolo[1,2-a]indoles, analogues of the mitomycin antibiotics.« less

Reaction pathways and free energy profiles for cholinesterase-catalyzed hydrolysis of 6-monoacetylmorphine

PubMed Central

Qiao, Yan; Han, Keli; Zhan, Chang-Guo

2014-01-01

As the most active metabolite of heroin, 6-monoacetylmorphine (6-MAM) can penetrate into the brain for the rapid onset of heroin effects. The primary enzymes responsible for the metabolism of 6-MAM to the less potent morphine in humans are acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). The detailed reaction pathways for AChE- and BChE-catalyzed hydrolysis of 6-MAM to morphine have been explored, for the first time, in the present study by performing first-principles quantum mechanical/molecular mechanical free energy calculations. It has been demonstrated that the two enzymatic reaction processes follow the similar catalytic reaction mechanism, and the whole catalytic reaction pathway for each enzyme consists of four reaction steps. According to the calculated results, the second reaction step associated with the transition state TS2a/TS2b should be rate-determining for the AChE/BChE-catalyzed hydrolysis, and the free energy barrier calculated for the AChE-catalyzed hydrolysis (18.3 kcal/mol) is 2.5 kcal/mol lower than that for the BChE-catalyzed hydrolysis (20.8 kcal/mol). The free energy barriers calculated for the AChE- and BChE-catalyzed reactions are in good agreement with the experimentally derived activation free energies (17.5 and 20.7 kcal/mol for the AChE- and BChE-catalyzed reactions, respectively). Further structural analysis reveals that the aromatic residues Phe295 and Phe297 in the acyl pocket of AChE (corresponding to Leu286 and Val288 in BChE) contribute to the lower energy of TS2a relative to TS2b. The obtained structural and mechanistic insights could be valuable for use in future rational design of a novel therapeutic treatment of heroin abuse. PMID:24595354

Trypsin-catalyzed tandem reaction: one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones by in situ formed acetaldehyde.

PubMed

Xie, Zong-Bo; Wang, Na; Wu, Wan-Xia; Le, Zhang-Gao; Yu, Xiao-Qi

2014-01-20

A simple, mild, one-pot tandem method catalyzed by trypsin was developed for the synthesis of 3,4-dihydropyrimidin-2(1H)-ones by the Biginelli reaction of urea, β-dicarbonyl compounds, and in situ-formed acetaldehyde. Trypsin was found to display dual promiscuous functions to catalyze transesterification and the Biginelli reaction in sequence. Copyright © 2013 Elsevier B.V. All rights reserved.

Polymeric bionanocomposite cast thin films with in situ laccase-catalyzed polymerization of dopamine for biosensing and biofuel cell applications.

PubMed

Tan, Yueming; Deng, Wenfang; Li, Yunyong; Huang, Zhao; Meng, Yue; Xie, Qingji; Ma, Ming; Yao, Shouzhuo

2010-04-22

We report here on the facile preparation of polymer-enzyme-multiwalled carbon nanotubes (MWCNTs) cast films accompanying in situ laccase (Lac)-catalyzed polymerization for electrochemical biosensing and biofuel cell applications. Lac-catalyzed polymerization of dopamine (DA) as a new substrate was examined in detail by UV-vis spectroscopy, cyclic voltammetry, quartz crystal microbalance, and scanning electron microscopy. Casting the aqueous mixture of DA, Lac and MWCNTs on a glassy carbon electrode (GCE) yielded a robust polydopamine (PDA)-Lac-MWCNTs/GCE that can sense hydroquinone with 643 microA mM(-1) cm(-2) sensitivity and 20-nM detection limit (S/N = 3). The DA substrate yielded the best biosensing performance, as compared with aniline, o-phenylenediamine, or o-aminophenol as the substrate for similar Lac-catalyzed polymerization. Casting the aqueous mixture of DA, glucose oxidase (GOx), Lac, and MWCNTs on a Pt electrode yielded a robust PDA-GOx-Lac-MWCNTs/Pt electrode that exhibits glucose-detection sensitivity of 68.6 microA mM(-1) cm(-2). In addition, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) was also coimmobilized to yield a PDA-Lac-MWCNTs-ABTS/GCE that can effectively catalyze the reduction of O(2), and it was successfully used as the biocathode of a membraneless glucose/O(2) biofuel cell (BFC) in pH 5.0 Britton-Robinson buffer. The proposed biomacromolecule-immobilization platform based on enzyme-catalyzed polymerization may be useful for preparing many other multifunctional polymeric bionanocomposites for wide applications.

A new route to methyl (R,E)-(-)-tetradeca-2,4,5-trienoate (pheromone of Acanthoscelides obtectus) utilizing a palladium-catalyzed asymmetric allene formation reaction.

PubMed

Ogasawara, Masamichi; Nagano, Takashi; Hayashi, Tamio

2005-07-08

[reaction: see text] A formal total synthesis of the sex attractant of male dried bean beetle, methyl (R,E)-(-)-tetradeca-2,4,5-trienoate, was achieved by a new efficient route utilizing the Pd-catalyzed asymmetric allene synthesis reaction. It was found that the atropisomeric biaryl bisphosphine (R)-segphos showed better enantioselectivity than (R)-binap in the Pd-catalyzed reaction for preparing alkyl-substituted axially chiral allenes.

Identification of activities that catalyze the cis-trans isomerization of the double bond of a mono-unsaturated fatty acid in Pseudomonas sp. strain E-3.

PubMed

Okuyama, H; Enari, D; Shibahara, A; Yamamoto, K; Morita, N

1996-06-01

A cell-free extract of Pseudomonas sp. strain E-3 catalyzed the conversion of 9-cis-hexadecenoic acid [16:1(9c)] to 9-trans-hexadecenoic acid [16:1(9t)] in the free acid form and when 16:1(9c) was esterified to phosphatidylethanolamine (PE). The cytosolic fraction catalyzed the isomerizations of free 16:1(9c) by itself and of 16:1(9c) esterified to PE in the presence of the membrane fraction. Tracer experiments using [2,2-2H2]16:1(9c) demonstrated that the isomerization of free 16:1(9c) occurred independently of the isomerization of 16:1(9c) esterified to PE, indicating that this bacterium has two types of activities that catalyze the cis-trans isomerization of the double bond of a mono-unsaturated fatty acid.

Metal centers in the anaerobic microbial metabolism of CO and CO2.

PubMed

Bender, Güneş; Pierce, Elizabeth; Hill, Jeffrey A; Darty, Joseph E; Ragsdale, Stephen W

2011-08-01

Carbon dioxide and carbon monoxide are important components of the carbon cycle. Major research efforts are underway to develop better technologies to utilize the abundant greenhouse gas, CO(2), for harnessing 'green' energy and producing biofuels. One strategy is to convert CO(2) into CO, which has been valued for many years as a synthetic feedstock for major industrial processes. Living organisms are masters of CO(2) and CO chemistry and, here, we review the elegant ways that metalloenzymes catalyze reactions involving these simple compounds. After describing the chemical and physical properties of CO and CO(2), we shift focus to the enzymes and the metal clusters in their active sites that catalyze transformations of these two molecules. We cover how the metal centers on CO dehydrogenase catalyze the interconversion of CO and CO(2) and how pyruvate oxidoreductase, which contains thiamin pyrophosphate and multiple Fe(4)S(4) clusters, catalyzes the addition and elimination of CO(2) during intermediary metabolism. We also describe how the nickel center at the active site of acetyl-CoA synthase utilizes CO to generate the central metabolite, acetyl-CoA, as part of the Wood-Ljungdahl pathway, and how CO is channelled from the CO dehydrogenase to the acetyl-CoA synthase active site. We cover how the corrinoid iron-sulfur protein interacts with acetyl-CoA synthase. This protein uses vitamin B(12) and a Fe(4)S(4) cluster to catalyze a key methyltransferase reaction involving an organometallic methyl-Co(3+) intermediate. Studies of CO and CO(2) enzymology are of practical significance, and offer fundamental insights into important biochemical reactions involving metallocenters that act as nucleophiles to form organometallic intermediates and catalyze C-C and C-S bond formations.

Metal centers in the anaerobic microbial metabolism of CO and CO2

PubMed Central

Bender, Güneş; Pierce, Elizabeth; Hill, Jeffrey A.; Darty, Joseph E.

2014-01-01

Carbon dioxide and carbon monoxide are important components of the carbon cycle. Major research efforts are underway to develop better technologies to utilize the abundant greenhouse gas, CO2, for harnessing ‘green’ energy and producing biofuels. One strategy is to convert CO2 into CO, which has been valued for many years as a synthetic feedstock for major industrial processes. Living organisms are masters of CO2 and CO chemistry and, here, we review the elegant ways that metalloenzymes catalyze reactions involving these simple compounds. After describing the chemical and physical properties of CO and CO2, we shift focus to the enzymes and the metal clusters in their active sites that catalyze transformations of these two molecules. We cover how the metal centers on CO dehydrogenase catalyze the interconversion of CO and CO2 and how pyruvate oxidoreductase, which contains thiamin pyrophosphate and multiple Fe4S4 clusters, catalyzes the addition and elimination of CO2 during intermediary metabolism. We also describe how the nickel center at the active site of acetyl-CoA synthase utilizes CO to generate the central metabolite, acetyl-CoA, as part of the Wood-Ljungdahl pathway, and how CO is channelled from the CO dehydrogenase to the acetyl-CoA synthase active site. We cover how the corrinoid iron–sulfur protein interacts with acetyl-CoA synthase. This protein uses vitamin B12 and a Fe4S4 cluster to catalyze a key methyltransferase reaction involving an organometallic methyl-Co3+ intermediate. Studies of CO and CO2 enzymology are of practical significance, and offer fundamental insights into important biochemical reactions involving metallocenters that act as nucleophiles to form organometallic intermediates and catalyze C–C and C–S bond formations. PMID:21647480

Chemiluminescence of off-line and on-line gold nanoparticle-catalyzed luminol system in the presence of flavonoid.

PubMed

Wu, Dong; Zhang, Xiaoyue; Liu, Yong; Ma, Yan; Wang, Xiaowu; Wang, Xiaojuan; Xu, Liuxin

2017-06-01

It was found that flavonoids could remarkably inhibit the chemiluminescence (CL) intensity of an off-line gold nanoparticle (AuNP)-catalyzed luminol-H 2 O 2 CL system. By contrast, flavonoids enhanced the CL intensity of an on-line AuNP-catalyzed luminol-H 2 O 2 CL system. In the off-line system, the AuNPs were prepared beforehand, whereas in the on-line system, AuNPs were produced by on-line mixing of luminol prepared in a buffer solution of NaHCO 3  - Na 2 CO 3 and HAuCl 4 with no need for the preliminary preparation of AuNPs. The on-line system had prominent advantages over the off-line system, namely a lowering of the background noise and improvements in the stability of the CL system. The results show that differences in the signal suppression effect of flavonoids on the off-line AuNP-catalyzed CL system are influenced by the combined action of a free radical scavenging effect and occupy-sites function; the latter was proved to be predominant using controlled experiments. Enhancement of the on-line system was ascribed to the presence of flavonoids promoting the on-line formation of AuNPs, which better catalyzed the luminol-H 2 O 2 CL reaction, and the enhancement activity of the six flavonoids increased with the increase in reducibility. This work broadens the scope of practical applications of an AuNP-catalyzed CL system. Copyright © 2016 John Wiley & Sons, Ltd.

Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes.

PubMed

Liu, Richard Y; Bae, Minwoo; Buchwald, Stephen L

2018-02-07

Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.

Regio-selectivity of the Oxidative C-S Bond Formation in Ergothioneine and Ovothiol Biosyntheses

PubMed Central

Song, Heng; Leninger, Maureen; Lee, Norman

2014-01-01

Ergothioneine (5) and ovothiol (8) are two novel thiol-containing natural products. Their C-S bonds are formed by oxidative coupling reactions catalyzed by EgtB and OvoA enzymes, respectively. In this work, it was discovered that besides catalyzing the oxidative coupling between histidine and cysteine (1 → 6 conversion), OvoA can also catalyze a direct oxidative coupling between hercynine (2) and cysteine (2 → 4 conversion), which can shorten the ergothioneine biosynthetic pathway by two steps. PMID:24016264

UPLC-MS/MS Method for Simultaneous Determination of Three Major Metabolites of Mequindox in Holothurian

PubMed Central

Liu, Huihui; Han, Dianfeng; Huang, Hui; Xu, Yingjiang; Gong, Xianghong

2018-01-01

This study developed an ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the detection of three major metabolites of mequindox, including 3-methyl-quinoxaline-2-carboxylic acid, 1-desoxymequindox, and 1,4-bisdesoxymequindox (MQCA, 1-DMEQ, and BDMEQ), in holothurian. Target analytes were simplified with ultrasound-assisted acidolysis extracted without complicated enzymolysis steps. After that, each sample was centrifuged and purified by an Oasis MAX cartridge. Then, the processed samples were separated and monitored by UPLC-MS/MS. This developed method has been validated according to FDA criteria. At fortified levels of 2, 10, and 20 μg/kg, recoveries ranged from 82.5% to 93.5% with the intraday RSD less than 7.27% and interday RSD less than 11.8%. The limit of detection (LOD) of all the three metabolites ranged from 0.21 to 0.48 μg/kg, while the limit of quantification (LOQ) ranged from 0.79 to 1.59 μg/kg. On application to commercial samples, 14 of 20 samples were detected positive for the three target analytes, with positive rate at 70 percentage. The result indicated that this method was specific, sensitive, and suitable for the quantification and conformation of the three major metabolites of MEQ in holothurian. PMID:29805832

UPLC-MS/MS Method for Simultaneous Determination of Three Major Metabolites of Mequindox in Holothurian.

PubMed

Liu, Huihui; Ren, Chuanbo; Han, Dianfeng; Huang, Hui; Zou, Rongjie; Zhang, Huawei; Xu, Yingjiang; Gong, Xianghong; Zhang, Xiuzhen; Li, Yanshen

2018-01-01

This study developed an ultraperformance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the detection of three major metabolites of mequindox, including 3-methyl-quinoxaline-2-carboxylic acid, 1-desoxymequindox, and 1,4-bisdesoxymequindox (MQCA, 1-DMEQ, and BDMEQ), in holothurian. Target analytes were simplified with ultrasound-assisted acidolysis extracted without complicated enzymolysis steps. After that, each sample was centrifuged and purified by an Oasis MAX cartridge. Then, the processed samples were separated and monitored by UPLC-MS/MS. This developed method has been validated according to FDA criteria. At fortified levels of 2, 10, and 20  μ g/kg, recoveries ranged from 82.5% to 93.5% with the intraday RSD less than 7.27% and interday RSD less than 11.8%. The limit of detection (LOD) of all the three metabolites ranged from 0.21 to 0.48  μ g/kg, while the limit of quantification (LOQ) ranged from 0.79 to 1.59  μ g/kg. On application to commercial samples, 14 of 20 samples were detected positive for the three target analytes, with positive rate at 70 percentage. The result indicated that this method was specific, sensitive, and suitable for the quantification and conformation of the three major metabolites of MEQ in holothurian.

Molybdenum Nitrogenase Catalyzes the Reduction and Coupling of CO to Form Hydrocarbons*♦

PubMed Central

Yang, Zhi-Yong; Dean, Dennis R.; Seefeldt, Lance C.

2011-01-01

The molybdenum-dependent nitrogenase catalyzes the multi-electron reduction of protons and N2 to yield H2 and 2NH3. It also catalyzes the reduction of a number of non-physiological doubly and triply bonded small molecules (e.g. C2H2, N2O). Carbon monoxide (CO) is not reduced by the wild-type molybdenum nitrogenase but instead inhibits the reduction of all substrates catalyzed by nitrogenase except protons. Here, we report that when the nitrogenase MoFe protein α-Val70 residue is substituted by alanine or glycine, the resulting variant proteins will catalyze the reduction and coupling of CO to form methane (CH4), ethane (C2H6), ethylene (C2H4), propene (C3H6), and propane (C3H8). The rates and ratios of hydrocarbon production from CO can be adjusted by changing the flux of electrons through nitrogenase, by substitution of other amino acids located near the FeMo-cofactor, or by changing the partial pressure of CO. Increasing the partial pressure of CO shifted the product ratio in favor of the longer chain alkanes and alkenes. The implications of these findings in understanding the nitrogenase mechanism and the relationship to Fischer-Tropsch production of hydrocarbons from CO are discussed. PMID:21454640

An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.

PubMed

DeKorver, Kyle A; Hsung, Richard P; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C

2012-06-15

A cascade of Pd-catalyzed N-to-C allyl transfer-intramolecular ketenimine-[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines.

Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition of 1-yne/ene-vinylcyclopropanes and CO: homologous Pauson-Khand reaction and total synthesis of (+/-)-alpha-agarofuran.

PubMed

Jiao, Lei; Lin, Mu; Zhuo, Lian-Gang; Yu, Zhi-Xiang

2010-06-04

A novel Rh(I)-catalyzed [(3 + 2) + 1] cycloaddition, which can be regarded as a homologous Pauson-Khand reaction, was developed to synthesize bicyclic cyclohexenones and cyclohexanones, enabling a new approach for synthesis of six-membered carbocycles ubiquitously found in natural products and pharmaceutics. The significance of the Rh-catalyzed [(3 + 2) + 1] cycloaddition has been demonstrated by the total synthesis of a furanoid sesquiterpene natural product, alpha-agarofuran, in which the bicyclic skeleton was constructed by the [(3 + 2) + 1] reaction of 1-yne-VCP and CO.

Copper-catalyzed oxidative dimerizations of 3-N-hydroxy-aminoprop-1-enes to form 1,4-dihydroxy-2,3-diaminocyclohexanes with C2  symmetry.

PubMed

Ghorpade, Satish; Liu, Rai-Shung

2014-11-17

This work describes the one-step construction of complex and important molecular frameworks through copper-catalyzed oxidations of cheap tertiary amines. Copper-catalyzed aerobic oxidations of N-hydroxyaminopropenes to form C2 -symmetric N- and O-functionalized cyclohexanes are described. Such catalytic oxidations proceed with remarkable stereocontrol and high efficiency. Reductive cleavage of the two NO bonds of these products delivers 1,4-dihydroxy-2,3-diaminocyclohexanes, which are important skeletons of several bioactive molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A One-Pot Synthesis of Dibenzofurans from 6-Diazo-2-cyclohexenones.

PubMed

Zhao, Hua; Yang, Ke; Zheng, Hongyan; Ding, Ruichao; Yin, Fangjie; Wang, Ning; Li, Yun; Cheng, Bin; Wang, Huifei; Zhai, Hongbin

2015-12-04

A novel and efficient protocol for the rapid construction of dibenzofuran motifs from 6-diazo-2-cyclohexenone and ortho-haloiodobenzene has been developed. The process involves one-pot Pd-catalyzed cross-coupling/aromatization and Cu-catalyzed Ullmann coupling.

Copper-catalyzed tandem reactions of 1-(2-iodoary)-2-yn-1-ones with isocyanides for the synthesis of 4-oxo-indeno[1,2-b]pyrroles.

PubMed

Cai, Qian; Zhou, Fengtao; Xu, Tianfeng; Fu, Liangbing; Ding, Ke

2011-01-21

A novel copper-catalyzed tandem reaction of 1-(2-iodoaryl)-2-yn-1-ones with isocyanides is described. The reaction is through a formal [3 + 2] cycloaddition/coupling tandem process and leads to efficient formation of 4-oxo-indeno[1,2-b]pyrroles.

Catalytic properties and heat stabilities of novel recombinant human N-acetyltransferase 2 allozymes support existence of genetic heterogeneity within the slow acetylator phenotype.

PubMed

Hein, David W; Doll, Mark A

2017-08-01

Human N-acetyltransferase 2 (NAT2) catalyzes the N-acetylation of numerous aromatic amine drugs such as sulfamethazine (SMZ) and hydrazine drugs such as isoniazid (INH). NAT2 also catalyzes the N-acetylation of aromatic amine carcinogens such as 2-aminofluorene and the O- and N,O-acetylation of aromatic amine and heterocyclic amine metabolites. Genetic polymorphism in NAT2 modifies drug efficacy and toxicity as well as cancer risk. Acetyltransferase catalytic activities and heat stability associated with six novel NAT2 haplotypes (NAT2*6C, NAT2*14C, NAT2*14D, NAT2*14E, NAT2*17, and NAT2*18) were compared with that of the reference NAT2*4 haplotype following recombinant expression in Escherichia coli. N-acetyltransferase activities towards SMZ and INH were significantly (p < 0.0001) lower when catalyzed by the novel recombinant human NAT2 allozymes compared to NAT2 4. SMZ and INH N-acetyltransferase activities catalyzed by NAT2 14C and NAT2 14D were significantly lower (p < 0.001) than catalyzed by NAT2 6C and NAT2 14E. N-Acetylation catalyzed by recombinant human NAT2 17 was over several hundred-fold lower than by recombinant NAT2 4 precluding measurement of its kinetic or heat inactivation constants. Similar results were observed for the O-acetylation of N-hydroxy-2-aminofluorene and N-hydroxy-2-amino-1-methyl-6-phenylimidazo [4,5-b] pyridine and the intramolecular N,O-acetylation of N-hydroxy-N-acetyl-2-aminofluorene. The apparent V max of the novel recombinant NAT2 allozymes NAT2 6C, NAT2 14C, NAT2 14D, and NAT2 14E towards AF, 4-aminobiphenyl (ABP), and 3,2'-dimethyl-4-aminobiphenyl (DMABP) were each significantly (p < 0.001) lower while their apparent K m values did not differ significantly (p > 0.05) from recombinant NAT2 4. The apparent V max catalyzed by NAT2 14C and NAT2 14D were significantly lower (p < 0.05) than the apparent V max catalyzed by NAT2 6C and NAT2 14E towards AF, ABP, and DMABP. Heat inactivation rate constants for recombinant human NAT2 14C, 14D, 14E, and 18 were significantly (p < 0.05) higher than NAT2 4. These results provide further evidence of genetic heterogeneity within the NAT2 slow acetylator phenotype.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

Cu-catalyzed aerobic oxidative cyclizations of 3-N-hydroxyamino-1,2-propadienes with alcohols, thiols, and amines to form α-O-, S-, and N-substituted 4-methylquinoline derivatives.

PubMed

Sharma, Pankaj; Liu, Rai-Shung

2015-03-16

A one-pot, two-step synthesis of α-O-, S-, and N-substituted 4-methylquinoline derivatives through Cu-catalyzed aerobic oxidations of N-hydroxyaminoallenes with alcohols, thiols, and amines is described. This reaction sequence involves an initial oxidation of N-hydroxyaminoallenes with NuH (Nu = OH, OR, NHR, and SR) to form 3-substituted 2-en-1-ones, followed by Brønsted acid catalyzed intramolecular cyclizations of the resulting products. Our mechanistic analysis suggests that the reactions proceed through a radical-type mechanism rather than a typical nitrone-intermediate route. The utility of this new Cu-catalyzed reaction is shown by its applicability to the synthesis of several 2-amino-4-methylquinoline derivatives, which are known to be key precursors to several bioactive molecules. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Intramolecular [2 + 2] Cycloaddition of Ketenimines via Palladium-Catalyzed Rearrangements of N-Allyl-Ynamides

PubMed Central

DeKorver, Kyle A.; Song, Wang-Ze; Wang, Xiao-Na; Walton, Mary C.

2012-01-01

A cascade of Pd-catalyzed N-to-C allyl transfer–intramolecular ketenimine–[2 + 2] cycloadditions of N-allyl ynamides is described. This tandem sequence is highly stereoselective and the [2 + 2] cycloaddition could be rendered in a crossed or fused manner depending on alkene substitutions, leading to bridged and fused bicycloimines. PMID:22667819

Copper-catalyzed one-pot synthesis of 1,2,4-triazoles from nitriles and hydroxylamine.

PubMed

Xu, Hao; Ma, Shuang; Xu, Yuanqing; Bian, Longxiang; Ding, Tao; Fang, Xiaomin; Zhang, Wenkai; Ren, Yanrong

2015-02-06

A simple and efficient copper-catalyzed one-pot synthesis of substituted 1,2,4-triazoles through reactions of two nitriles with hydroxylamine has been developed. The protocol uses simple and readily available nitriles and hydroxylamine hydrochloride as the starting materials and inexpensive Cu(OAc)2 as the catalyst, and the corresponding 1,2,4-triazole derivatives are obtained in moderate to good yields. The reactions include sequential intermolecular addition of hydroxylamine to one nitrile to provide amidoxime, copper-catalyzed treatment of the amidoxime with another nitrile, and intramolecular dehydration/cyclization. This finding provides a new and useful strategy for synthesis of 1,2,4-triazole derivatives.

Rhodium enalcarbenoids: direct synthesis of indoles by rhodium(II)-catalyzed [4+2] benzannulation of pyrroles.

PubMed

Dawande, Sudam Ganpat; Kanchupalli, Vinaykumar; Kalepu, Jagadeesh; Chennamsetti, Haribabu; Lad, Bapurao Sudam; Katukojvala, Sreenivas

2014-04-14

Disclosed herein is the design of an unprecedented electrophilic rhodium enalcarbenoid which results from rhodium(II)-catalyzed decomposition of a new class of enaldiazo compounds. The synthetic utility of these enalcarbenoids has been successfully demonstrated in the first transition-metal-catalyzed [4+2] benzannulation of pyrroles, thus leading to substituted indoles. The new benzannulation has been applied to the efficient synthesis of the natural product leiocarpone as well as a potent adipocyte fatty-acid binding protein inhibitor. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Two-Component para-Nitrophenol Monooxygenase Initiates a Novel 2-Chloro-4-Nitrophenol Catabolism Pathway in Rhodococcus imtechensis RKJ300

PubMed Central

Min, Jun; Zhang, Jun-Jie

2015-01-01

Rhodococcus imtechensis RKJ300 (DSM 45091) grows on 2-chloro-4-nitrophenol (2C4NP) and para-nitrophenol (PNP) as the sole carbon and nitrogen sources. In this study, by genetic and biochemical analyses, a novel 2C4NP catabolic pathway different from those of all other 2C4NP utilizers was identified with hydroxyquinol (hydroxy-1,4-hydroquinone or 1,2,4-benzenetriol [BT]) as the ring cleavage substrate. Real-time quantitative PCR analysis indicated that the pnp cluster located in three operons is likely involved in the catabolism of both 2C4NP and PNP. The oxygenase component (PnpA1) and reductase component (PnpA2) of the two-component PNP monooxygenase were expressed and purified to homogeneity, respectively. The identification of chlorohydroquinone (CHQ) and BT during 2C4NP degradation catalyzed by PnpA1A2 indicated that PnpA1A2 catalyzes the sequential denitration and dechlorination of 2C4NP to BT and catalyzes the conversion of PNP to BT. Genetic analyses revealed that pnpA1 plays an essential role in both 2C4NP and PNP degradations by gene knockout and complementation. In addition to catalyzing the oxidation of CHQ to BT, PnpA1A2 was also found to be able to catalyze the hydroxylation of hydroquinone (HQ) to BT, revealing the probable fate of HQ that remains unclear in PNP catabolism by Gram-positive bacteria. This study fills a gap in our knowledge of the 2C4NP degradation mechanism in Gram-positive bacteria and also enhances our understanding of the genetic and biochemical diversity of 2C4NP catabolism. PMID:26567304

Zeolite 5A Catalyzed Etherification of Diphenylmethanol

ERIC Educational Resources Information Center

Cooke, Jason; Henderson, Eric J.; Lightbody, Owen C.

2009-01-01

An experiment for the synthetic undergraduate laboratory is described in which zeolite 5A catalyzes the room temperature dehydration of diphenylmethanol, (C[subscript 6]H[subscript 5])[subscript 2]CHOH, producing 1,1,1',1'-tetraphenyldimethyl ether, (C[subscript 6]H[subscript 5])[subscript 2]CHOCH(C[subscript 6]H[subscript 5])[subscript 2]. The…

Iron-Catalyzed Intramolecular C(sp(2))-N Cyclization of 1-(N-Arylpyrrol-2-yl)ethanone O-Acetyl Oximes toward Pyrrolo[1,2-a]quinoxaline Derivatives.

PubMed

Zhang, Zhiguo; Li, Junlong; Zhang, Guisheng; Ma, Nana; Liu, Qingfeng; Liu, Tongxin

2015-07-02

An efficient and convenient iron-catalyzed protocol has been developed for the synthesis of substituted pyrrolo[1,2-a]quinoxalines from 1-(N-arylpyrrol-2-yl)ethanone O-acetyl oximes through N-O bond cleavage and intramolecular directed C-H arylation reactions in acetic acid.

Palladium-catalyzed cocyclotrimerization of arynes with a pyramidalized alkene.

PubMed

Alonso, José M; Quiroga, Sabela; Codony, Sandra; Turcu, Andreea L; Barniol-Xicota, Marta; Pérez, Dolores; Guitián, Enrique; Vázquez, Santiago; Peña, Diego

2018-05-23

The metal-catalyzed [2+2+2] cocycloaddition of arynes with pyramidalized alkenes is presented. The generation of a highly reactive pyramidalized alkene in the presence of a large excess of in situ-produced arynes led to the corresponding cocyclotrimerization (1 : 2)-adducts in good yields, establishing the first example of a palladium-based reaction of a pyramidalized alkene.

Zinc-catalyzed allenylations of aldehydes and ketones.

PubMed

Fandrick, Daniel R; Saha, Jaideep; Fandrick, Keith R; Sanyal, Sanjit; Ogikubo, Junichi; Lee, Heewon; Roschangar, Frank; Song, Jinhua J; Senanayake, Chris H

2011-10-21

The general zinc-catalyzed allenylation of aldehydes and ketones with an allenyl boronate is presented. Preliminary mechanistic studies support a kinetically controlled process wherein, after a site-selective B/Zn exchange to generate a propargyl zinc intermediate, the addition to the electrophile effectively competes with propargyl-allenyl zinc equilibration. The utility of the methodology was demonstrated by application to a rhodium-catalyzed [4+2] cycloaddition. © 2011 American Chemical Society

Computational Elucidation of Selectivities and Mechanisms Performed by Organometallic and Bioinorganic Catalysts

NASA Astrophysics Data System (ADS)

Grandner, Jessica Marie

Computational methods were used to determine the mechanisms and selectivities of organometallic-catalyzed reactions. The first half of the dissertation focuses on the study of metathesis catalysts in collaboration with the Grubbs group at CalTech. Chapter 1 describes the studies of the decomposition modes of several ruthenium-based metathesis catalysts. These studies were performed to better understand the decomposition of such catalysts in order to prevent decomposition (Chapter 1.2) or utilize decomposed catalysts for alternative reactions (Chapter 1.1). Chapter 2.1 describes the computational investigation of the origins of stereoretentive metathesis with ruthenium-based metathesis catalysts. These findings were then used to computationally design E-selective metathesis catalysts (Chapter 2.2). While the first half of the dissertation was centered around ruthenium catalysts, the second half of the dissertation pertains to iron-catalyzed reaction, in particular, iron-catalyzed reactions by P450 enzymes. The elements of Chapter 3 concentrate on the stereo- and chemo-selectivity of P450-catalyzed C-H hydroxylations. By combining multiple computational methods, the inherent activity of the iron-oxo catalyst and the influence of the active site on such reactions were illuminated. These discoveries allow for the engineering of new substrates and mutant enzymes for tailored C-H hydroxylation. While the mechanism of C-H hydroxylations catalyzed by P450 enzymes has been well studied, there are several P450-catalyzed transformations for which the mechanism is unknown. The components of Chapter 4 describe the use of computations to determine the mechanisms of complex, multi-step reactions catalyzed by P450s. The determination of these mechanisms elucidates how these enzymes react with various functional groups and substrate architectures and allows for a better understanding of how drug-like compounds may be broken down by human P450s.

Studies on the oxidation reaction of tyrosine (Tyr) with H2O2 catalyzed by horseradish peroxidase (HRP) in alcohol-water medium by spectrofluorimetry and differential spectrophotometry.

PubMed

Tang, Bo; Wang, Yan; Liang, Huiling; Chen, Zhenzhen; He, Xiwen; Shen, Hanxi

2006-03-01

An oxidation reaction of tyrosine (Tyr) with H(2)O(2) catalyzed by horseradish peroxidase (HRP) was studied by spectrofluorimetry and differential spectrophotometry in the alcohol(methanol, ethanol, 1-propanol and isopropanol)-water mutual solubility system. Compared with the enzymatic-catalyzed reaction in the water medium, the fluorescence intensities of the product weakened, even extinguished. Because the addition of alcohols made the conformation of HRP change, the catalytic reaction shifted to the side of polymerization and the polymer (A(n)H(2), n>or=3) exhibited no fluorescence. The four alcohols cannot deactivate HRP. Moreover isopropanol activated HRP remarkably.

Binding Energy and Catalysis by D-Xylose Isomerase: Kinetic, Product and X-Ray Crystallographic Analysis of Enzyme-Catalyzed Isomerization of (R)-Glyceraldehyde‡, ¶

PubMed Central

Toteva, Maria M.; Silvaggi, Nicholas R.; Allen, Karen N.; Richard, John P.

2011-01-01

D-Xylose isomerase (XI) and triosephosphate isomerase (TIM) catalyze the aldose-ketose isomerization reactions of D-xylose and D-glyceraldehyde 3-phosphate (DGAP), respectively. D-Glyceraldehyde (DGA) is the triose fragment common to the substrates for XI and TIM. The XI-catalyzed isomerization of DGA to give dihydroxyacetone (DHA) in D2O was monitored by 1H NMR spectroscopy and kcat/Km = 0.034 M−1 s−1 was determined for this isomerization at pD 7.0. This is similar to kcat/Km = 0.017 M−1 s−1 for the TIM-catalyzed carbon deprotonation reaction of DGA in D2O at pD 7.0 [Amyes, T. L.; O’Donoghue, A. C. and Richard J. P. (2001) J. Am. Chem. Soc. 123, 11325–11326]. The much larger activation barrier for XI-catalyzed isomerization of D-xylose (kcat/Km = 490 M−1 s−1) than for the TIM-catalyzed isomerization of DGAP (kcat/Km = 9.6 x 106 M−1 s−1) is due to: (i) The larger barrier to conversion of cyclic D-xylose to the reactive linear sugar (5.4 kcal/mol) than for conversion of DGAP hydrate to the free aldehyde (1.7 kcal/mol). (ii) The smaller intrinsic binding energy [Jencks, W. P. (1975) Adv. Enzymol. Relat. Areas Mol. Biol. 43, 219–410] of the terminal ethylene glycol fragment of D-xylose (9.3 kcal/mol) than of the phosphodianion group of DGAP (ca. 12 kcal/mol). The XI-catalyzed isomerization of DGA in D2O at pD 7.0 gives a 90% yield of [1-1H]-DHA and a 10% yield of [1-2H]-DHA, the product of isomerization with deuterium incorporation from solvent D2O. By comparison, the transfer of 3H from labeled hexose substrate to solvent is observed only once in every 109 turnovers for the XI-catalyzed isomerization of [2-3H]-glucose in H2O [Allen, K. N., Lavie, A., Farber, G. K., Glasfeld, A., Petsko, G. A., and Ringe, D. (1994), Biochemistry 33, 1481–1487]. We propose that truncation of the terminal ethylene glycol fragment of D-xylose to give DGA results in a large decrease in the rate of XI-catalyzed isomerization with hydride transfer compared with that for proton transfer. An ultra-high resolution (0.97 Å) X-ray crystal structure was determined for the complex obtained by soaking crystals of XI with 50 mM DGA. The triose binds to XI as the unreactive hydrate, but ligand binding induces metal cofactor movement and conformational changes in active site residues similar to those observed for XI•sugar complexes. PMID:21995300

Nickel-catalyzed amination of aryl chlorides with ammonia or ammonium salts.

PubMed

Green, Rebecca A; Hartwig, John F

2015-03-16

The nickel-catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well-defined single-component nickel(0) precatalyst containing a Josiphos ligand and an η(2)-bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Identification of UGT2B9*2 and UGT2B33 isolated from female rhesus monkey liver.

PubMed

Dean, Brian; Arison, Byron; Chang, Steve; Thomas, Paul E; King, Christopher

2004-06-01

Two UDP-glucuronosyltransferases (UGT2B9(*)2 and UGT2B33) have been isolated from female rhesus monkey liver. Microsomal preparations of the cell lines expressing the UGTs catalyzed the glucuronidation of the general substrate 7-hydroxy-4-(trifluoromethyl)coumarin in addition to selected estrogens (beta-estradiol and estriol) and opioids (morphine, naloxone, and naltrexone). UGT2B9(*)2 displayed highest efficiency for beta-estradiol-17-glucuronide production and did not catalyze the glucuronidation of naltrexone. UGT2B33 displayed highest efficiency for estriol and did not catalyze the glucuronidation of beta-estradiol. UGT2B9(*)2 was found also to catalyze the glucuronidation of 4-hydroxyestrone, 16-epiestriol, and hyodeoxycholic acid, while UGT2B33 was capable of conjugating 4-hydroxyestrone, androsterone, diclofenac, and hyodeoxycholic acid. Three glucocorticoids (cortisone, cortisol, and corticosterone) were not substrates for glucuronidation by liver or kidney microsomes or any expressed UGTs. Our current data suggest the use of beta-estradiol-3-glucuronidation, beta-estradiol-17-glucuronidation, and estriol-17-glucuronidation to assay UGT1A01, UGT2B9(*)2, and UGT2B33 activity in rhesus liver microsomes, respectively.

Enantioselective Reduction of Ketones Catalyzed by Rare-Earth Metals Complexed with Phenoxy Modified Chiral Prolinols.

PubMed

Song, Peng; Lu, Chengrong; Fei, Zenghui; Zhao, Bei; Yao, Yingming

2018-06-01

Enantioselective reduction of ketones and α,β-unsaturated ketones by pinacolborane (HBpin) has been well-established by using chiral rare-earth metal catalysts with phenoxy modified prolinols. A number of highly optically active alcohols were obtained from reduction of simple ketones catalyzed by ytterbium complex 1 [L 4 Yb(L 4 H)] (H 2 L 4 = ( S)-2- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol). Moreover, α,β-unsaturated ketones were selectively reduced to a wide range of chiral allylic alcohols with excellent yields, high enantioselectivity, and complete chemoselectivity, catalyzed by a single component chiral ytterbium complex 2 [L 1 Yb(L 1 H)] (H 2 L 1 = ( S)-2,4-di- tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol).

Ruthenium-catalyzed regioselective allylic amination of 2,3,3-trifluoroallylic carbonates.

PubMed

Isobe, Shin-Ichi; Terasaki, Shou; Hanakawa, Taisyun; Mizuno, Shota; Kawatsura, Motoi

2017-04-05

We demonstrated the ruthenium-catalyzed allylic amination of 2,3,3-trifluoroallylic carbonates with several types of amines. The reactions proceeded with several types of amines, and succeeded in obtaining polyfluorinated terminal alkenes possessing branched allylic amines as a single regioisomer.

Intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes†

PubMed Central

Andrew Evans, P.; Sawyer, James R.; Lai, Kwong Wah; Huffman, John C.

2006-01-01

The crossed intermolecular rhodium-catalyzed [2 + 2 + 2] carbocyclization of carbon and heteroatom tethered 1,6-enynes can be accomplished with symmetrical and unsymmetrical alkynes, to afford the corresponding bicyclohexadienes in an efficient and highly selective manner. PMID:16075089

A Catalytic Asymmetric Synthesis of Polysubstituted Piperidines Using a Rhodium (I) Catalyzed [2+2+2] Cycloaddition Employing a Cleavable Tether

PubMed Central

Martin, Timothy J.; Rovis, Tomislav

2013-01-01

An enantioselective rhodium (I) catalyzed [2+2+2] cycloaddition with a cleavable tether has been developed. The reaction proceeds with a variety of alkyne substrates in good yield and high enantioselectivity. Upon reduction of the vinylogous amide in high diastereoselectivity (>19:1) and cleavage of the tether, N-methylpiperidine products with functional group handles can be accessed. PMID:23606664

Rhodium-Catalyzed Boron Arylation of 1,2-Azaborines**

PubMed Central

Rudebusch, Gabriel E.; Zakharov, Lev N.; Liu, Shih-Yuan

2013-01-01

A Sn-phony in B! BN isosteres of biphenyl compounds are prepared through Rh-catalyzed cross-coupling between 2-chloro-1,2-azaborines and arylstannanes (see scheme). The synthetic method should enable investigations of structure–activity relationships (SARs) by expanding the chemical space of the pharmaceutically relevant biphenyl structure through BN/CC isosterism. PMID:23832871

George A. Olah, Carbocation and Hydrocarbon Chemistry

Science.gov Websites

. Final Technical Report. [HF:BF{sub 2}/H{sub 2}] , DOE Technical Report, 1980 Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984 , DOE Technical Report, 1984 Superacid Catalyzed Coal Conversion Chemistry. Final Technical Report

Mechanistic diversity in the RuBisCO superfamily: RuBisCO from Rhodospirillum rubrum is not promiscuous for reactions catalyzed by RuBisCO-like proteins.

PubMed

Warlick, Benjamin P E; Imker, Heidi J; Sriram, Jaya; Tabita, F Robert; Gerlt, John A

2012-11-27

d-Ribulose 1,5-bisphosphate carboxylase/oxygenases (RuBisCOs) are promiscuous, catalyzing not only carboxylation and oxygenation of d-ribulose 1,5-bisphosphate but also other promiscuous, presumably nonphysiological, reactions initiated by abstraction of the 3-proton of d-ribulose 1,5-bisphosphate. Also, RuBisCO has homologues that do not catalyze carboxylation; these are designated RuBisCO-like proteins or RLPs. Members of the two families of RLPs catalyze reactions in the recycling of 5'-methylthioadenosine (MTA) generated by polyamine synthesis: (1) the 2,3-diketo-5-methylthiopentane 1-phosphate (DK-MTP 1-P) "enolase" reaction in the well-known "methionine salvage" pathway in Bacillus sp. and (2) the 5-methylthio-d-ribulose 1-phosphate (MTRu 1-P) 1,3-isomerase reaction in the recently discovered "MTA-isoprenoid shunt" that generates 1-deoxy-d-xylulose 5-phosphate for nonmevalonate isoprene synthesis in Rhodospirillum rubrum. We first studied the structure and reactivity of DK-MTP 1-P that was reported to decompose rapidly [Ashida, H., Saito, Y., Kojima, C., and Yokota, A. (2008) Biosci., Biotechnol., Biochem. 72, 959-967]. The 2-carbonyl group of DK-MTP 1-P is rapidly hydrated and can undergo enolization both nonenzymatically and enzymatically via the small amount of unhydrated material that is present. We then examined the ability of RuBisCO from R. rubrum to catalyze both of the RLP-catalyzed reactions. Contrary to a previous report [Ashida, H., Saito, Y., Kojima, C., Kobayashi, K., Ogasawara, N., and Yokota, A. (2003) Science 302, 286-290], we were unable to confirm that this RuBisCO catalyzes the DK-MTP 1-P "enolase" reaction either in vitro or in vivo. We also determined that this RuBisCO does not catalyze the MTRu 1-P 1,3-isomerase reaction in vitro. Thus, although RuBisCOs can be functionally promiscuous, RuBisCO from R. rubrum is not promiscuous for either of the known RLP-catalyzed reactions.

A Rhodium(I)-Xylyl-BINAP Catalyzed Asymmetric Ynamide-[2 + 2 + 2] Cycloaddition in the Synthesis of Optically Enriched N,O-Biaryls

PubMed Central

Oppenheimer, Jossian; Johnson, Whitney L.; Figueroa, Ruth; Hayashi, Ryuji; Hsung, Richard P.

2009-01-01

A rhodium(I)-xylyl-BINAP catalyzed asymmetric [2 + 2 + 2] cycloaddition of achiral conjugated aryl ynamides with various diynes is described here. This asymmetric cycloaddition provides a series of structurally interesting chiral N,O-biaryls with excellent enantioselectivity along with a modest diastereoselectivity with respect to both C-C and C-N axial chirality. PMID:20161177

Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

PubMed

Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

2015-12-09

The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

Development of melamine modified urea formaldehyde resins based o nstrong acidic pH catalyzed urea formaldehyde polymer

Treesearch

Chung-Yun Hse

2009-01-01

To upgrade the performance of urea-formaldehyde (UF) resin bonded particleboards, melamine modified urea-formaldehyde (MUF) resins based on strong acidic pH catalyzed UF polymers were investigated. The study was conducted in a series of two experiments: 1) formulation of MUF resins based on a UF polymer catalyzed with strong acidic pH and 2) determination of the...

Copper-catalyzed synthesis of substituted furans and pyrroles by heterocyclodehydration and tandem heterocyclodehydration-hydration of 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives.

PubMed

Gabriele, Bartolo; Veltri, Lucia; Plastina, Pierluigi; Mancuso, Raffaella; Vetere, Mabel V; Maltese, Vito

2013-05-17

CuCl2-catalyzed heterocyclodehydration of readily available 3-yne-1,2-diols and 1-amino-3-yn-2-ol derivatives afforded substituted furans and pyrroles, respectively, in good to high yields (53-99%) under mild conditions (MeOH as the solvent, 80-100 °C, 1-24 h). In the case of 2,2-dialkynyl-1,2-diols, bearing an additional alkynyl substituent at C-2, a cascade process, corresponding to copper-catalyzed heterocyclodehydration followed by acid-catalyzed hydration of the triple bond, was realized when the reaction was carried out in the presence of both CuCl2 and TsOH, leading to 3-acylfurans in one step and high yields (75-84%). Under the same conditions, N-Boc-2-alkynyl-1-amino-3-yn-2-ols were converted into the corresponding N-unsubstituted 3-acylpyrroles in low to fair yields (19-59%). However, working in the presence of added water and a large excess of CO2 (40 atm), in addition to CuCl2 and TsOH, caused a significant improvement of the yields of 3-acylpyrroles (68-87%), thus making the method of general synthetic applicability.

Flavin-N5 Covalent Intermediate in a Nonredox Dehalogenation Reaction Catalyzed by an Atypical Flavoenzyme.

PubMed

Dai, Yumin; Kizjakina, Karina; Campbell, Ashley C; Korasick, David A; Tanner, John J; Sobrado, Pablo

2018-01-04

The flavin-dependent enzyme 2-haloacrylate hydratase (2-HAH) catalyzes the conversion of 2-chloroacrylate, a major component in the manufacture of acrylic polymers, to pyruvate. The enzyme was expressed in Escherichia coli, purified, and characterized. 2-HAH was shown to be monomeric in solution and contained a non-covalent, yet tightly bound, flavin adenine dinucleotide (FAD). Although the catalyzed reaction was redox-neutral, 2-HAH was active only in the reduced state. A covalent flavin-substrate intermediate, consistent with the flavin-acrylate iminium ion, was trapped with cyanoborohydride and characterized by mass spectrometry. Small-angle X-ray scattering was consistent with 2-HAH belonging to the succinate dehydrogenase/fumarate reductase family of flavoproteins. These studies establish 2-HAH as a novel noncanonical flavoenzyme. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt/rhodium heterobimetallic nanoparticle-catalyzed carbonylative [2+2+1] cycloaddition of allenes and bisallenes to Pauson-Khand-type reaction products.

PubMed

Park, Ji Hoon; Kim, Eunha; Kim, Hyeong-Mook; Choi, Soo Young; Chung, Young Keun

2008-05-28

The first catalytic intra- and intermolecular [2+2+1] cocyclization reactions of allenes and carbon monoxide have been developed. In the Co(2)Rh(2) heterobimetallic nanoparticle-catalyzed carbonylative [2+2+1] cycloaddition of allenes and carbon monoxide, the allenes formally serve both as an excellent alkene- and alkyne-like moiety within a Pauson-Khand-type process.

Copper-Catalyzed Tandem Reactions for Synthesis of Pyrazolo[5,1-a]isoquinolines with Heterocyclic Ketene Aminals as Ligands.

PubMed

Wen, Li-Rong; Jin, Xian-Jun; Niu, Xiao-Dong; Li, Ming

2015-01-02

A CuI-catalyzed tandem reaction of 5-(2-bromoaryl)-N-aryl-1H-pyrazol-3-amines with active acetonitrile derivatives to prepare pyrazolo[5,1-a]isoquinolines in good to excellent yields has been successfully developed under mild conditions with heterocyclic ketene aminals (HKAs) as new ligands. This is the first time HKAs have been used as ligands for copper-catalyzed coupling reactions.

Palladium-catalyzed domino C,N-coupling/carbonylation/Suzuki coupling reaction: an efficient synthesis of 2-aroyl-/heteroaroylindoles.

PubMed

Arthuis, Martin; Pontikis, Renée; Florent, Jean-Claude

2009-10-15

A convenient one-pot synthesis of 2-aroylindoles using a domino palladium-catalyzed C,N-coupling/carbonylation/C,C-coupling sequence is described. The reaction involved easily prepared 2-gem-dibromovinylanilines and boronic acids under carbon monoxide. Optimized reaction conditions allowed the construction of a wide variety of highly functionalized 2-aroyl-/heteroaroylindoles in satisfactory yields.

Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

PubMed

Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

2018-06-29

The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Horseradish-Peroxidase-Catalyzed Tyrosine Click Reaction.

PubMed

Sato, Shinichi; Nakamura, Kosuke; Nakamura, Hiroyuki

2017-03-02

The efficiency of protein chemical modification on tyrosine residues with N-methylluminol derivatives was drastically improved by using horseradish peroxidase (HRP). In the previous method, based on the use of hemin and H 2 O 2 , oxidative side reactions such as cysteine oxidation were problematic for functionalization of proteins selectively on tyrosine residues. Oxidative activation of N-methylluminol derivatives with a minimum amount of H 2 O 2 prevented the occurrence of oxidative side reactions under HRP-catalyzed conditions. As probes for HRP-catalyzed protein modification, N-methylluminol derivatives showed much higher efficiency than tyramide without inducing oligomerization of probe molecules. Tyrosine modification also proceeded in the presence of β-nicotinamide adenine dinucleotide (NADH, H 2 O 2 -free conditions). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Assessing the Regioselectivity of OleD-Catalyzed Glycosylation with a Diverse Set of Acceptors

PubMed Central

Zhou, Maoquan; Hamza, Adel; Zhan, Chang-Guo; Thorson, Jon S.

2013-01-01

To explore the acceptor regioselectivity of OleD-catalyzed glucosylation, the products of OleD-catalyzed reactions with the six structurally diverse acceptors - flavones (daidzein), isoflavones (flavopiridol), stilbenes (resveratrol), indole alkaloids (10-hydroxycamptothecin), and steroids (2-methoxyestradiol) - were determined. This study highlights the first synthesis of flavopiridol and 2-methoxyestradiol glucosides and confirms the ability of OleD to glucosylate both aromatic and aliphatic nucleophiles. In all cases, molecular dynamics simulations were consistent with the determined product distribution and suggest the potential to develop a virtual screening model to identify additional OleD substrates. PMID:23360118

Glycerol Dehydration to Acrolein Catalyzed by ZSM‐5 Zeolite in Supercritical Carbon Dioxide Medium

PubMed Central

Zou, Bin; Ren, Shoujie

2016-01-01

Abstract Supercritical carbon dioxide (SC‐CO2) has been used for the first time as a reaction medium for the dehydration of glycerol to acrolein catalyzed by a solid acid. Unprecedented catalyst stability over 528 hours of time‐on‐stream was achieved and the rate of coke deposition on the zeolite catalyst was the lowest among extensive previous studies, showing potential for industrial application. Coking pathways in SC‐CO2 were also elucidated for future development. The results have potential implications for other dehydration reactions catalyzed by solid acids. PMID:27796088

Nitrous oxide-forming codenitrification catalyzed by cytochrome P450nor.

PubMed

Su, Fei; Takaya, Naoki; Shoun, Hirofumi

2004-02-01

Intact cells of the denitrifying fungus Fusarium oxysporum were previously shown to catalyze codenitrification to form a hybrid nitrous oxide (N2O) species from nitrite and other nitrogen compounds such as azide and ammonia. Here we show that cytochrome P450nor can catalyze the codenitrification reaction to form N2O from nitric oxide (NO) but not nitrite, and azide or ammonia. The results show that the direct substrate of the codenitrification by intact cells should not be nitrite but NO, which is formed from nitrite by the reaction of a dissimilatory nitrite reductase.

Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O.

PubMed

Motokura, Ken; Kashiwame, Daiki; Miyaji, Akimitsu; Baba, Toshihide

2012-05-18

A copper-catalyzed formic acid synthesis from CO2 with hydrosilanes has been accomplished. The Cu(OAc)2·H2O-1,2-bis(diphenylphosphino)benzene system is highly effective for the formic acid synthesis under 1 atm of CO2. The TON value approached 8100 in 6 h. The reaction pathway was revealed by in situ NMR analysis and isotopic experiments.

Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

PubMed Central

Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F

2014-01-01

Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminating step. This work demonstrates the power of ruthenium-catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C—H functionalization steps taking place in a single operation to access novel carbocyclic structures. PMID:24453063

Characterization of 2-Oxindole Forming Heme Enzyme MarE, Expanding the Functional Diversity of the Tryptophan Dioxygenase Superfamily.

PubMed

Zhang, Yuyang; Zou, Yi; Brock, Nelson L; Huang, Tingting; Lan, Yingxia; Wang, Xiaozheng; Deng, Zixin; Tang, Yi; Lin, Shuangjun

2017-08-30

3-Substituted 2-oxindoles are important structural motifs found in many biologically active natural products and pharmaceutical lead compounds. Here, we report an enzymatic formation of the 3-substituted 2-oxindoles catalyzed by MarE in the maremycin biosynthetic pathway in Streptomyces sp. B9173. MarE is a homologue of Fe II /heme-dependent tryptophan 2,3-dioxygenases (TDOs). Typical TDOs usually catalyze the insertion of two oxygen atoms from O 2 into an indole ring to generate N-formylkynurenine (NFK)-like products. In contrast, MarE catalyzes the insertion of a single oxygen atom from O 2 into an indole ring, to probably generate an epoxyindole intermediate that undergoes an unprecedented 2,3-hydride migration to form 2-oxindole structure. MarE shows substrate robustness to catalyze the conversion of a series of 3-substituted indoles into their corresponding 3-substituted 2-oxindoles. Although containing most key amino acid residues conserved in well-known TDO homologues, MarE falls into a separate new subgroup in the phylogenetic tree. The characterization of MarE and its homologue enriches the functional diversities of TDO superfamily and provides a new strategy for discovering novel natural products containing 3-substituted 2-oxindole pharmacophores by genome mining.

Introducing the New Class of N-Phosphoryl Ynamides via Cu(I)-Catalyzed Amidations of Alkynyl Bromides

PubMed Central

Walton, Mary C.; North, Troy D.

2011-01-01

We describe here the first synthesis of N-phosphoryl ynamides featuring C- and P-chirality via copper(I)-catalyzed amidative cross-couplings between phosphoramidates and phosphordiamidates with alkynyl bromides. Also featured is a tandem aza-Claisen–hetero-[2+2] cycloaddition for the synthesis of N-phosphoryl azetidin-2-imines. PMID:21848304

Gold-catalyzed synthesis of benzil derivatives and α-keto imides via oxidation of alkynes.

PubMed

Xu, Cheng-Fu; Xu, Mei; Jia, Yi-Xia; Li, Chuan-Ying

2011-03-18

An efficient process based on the gold-catalyzed redox reaction has been developed to oxidize 1,2-diarylacetylene or ynamide to 1,2-diaryldiketone or α-keto imide respectively. This process can tolerate a variety of functional groups and affords 1,2-dicarbonyl compounds in excellent yields under mild reaction conditions.

Catalytic reduction of O2 by cytochrome C using a synthetic model of cytochrome C oxidase.

PubMed

Collman, James P; Ghosh, Somdatta; Dey, Abhishek; Decréau, Richard A; Yang, Ying

2009-04-15

Cytochrome c oxidase (CcO) catalyzes the four-electron reduction of oxygen to water, the one-electron reductant Cytochrome c (Cytc) being the source of electrons. Recently we reported a functional model of CcO that electrochemically catalyzes the four-electron reduction of O(2) to H(2)O (Collman et al. Science 2007, 315, 1565). The current paper shows that the same functional CcO model catalyzes the four-electron reduction of O(2) using the actual biological reductant Cytc in a homogeneous solution. Both single and steady-state turnover kinetics studies indicate that O(2) binding is rate-determining and that O-O bond cleavage and electron transfer from reduced Cytc to the oxidized model complex are relatively fast.

Ara h 2 cross-linking catalyzed by MTGase decreases its allergenicity.

PubMed

Wu, Zhihua; Lian, Jun; Zhao, Ruifang; Li, Kun; Li, Xin; Yang, Anshu; Tong, Ping; Chen, Hongbing

2017-03-22

Peanuts, whose major allergen is Ara h 2, are included among the eight major food allergens. After reduction using dithiothreitol (DTT), cross-linking of Ara h 2 could be catalyzed by microbial transglutaminase (MTGase), a widely used enzyme in the food industry. In this study, Ara h 2 cross-linking was catalyzed by MTGase after it was reduced by DTT. Using mass spectrometry and PLINK software, five cross-linkers were identified, and five linear allergen epitopes were found to be involved in the reactions. The IgE binding capacity of cross-linked Ara h 2 was found to be significantly lower compared to that of native and reduced Ara h 2. After simulated gastric fluid (SGF) digestion, the digested products of the cross-linked Ara h 2, again, had a significantly lower IgE binding capacity compared to untreated and reduced Ara h 2. Furthermore, reduced and cross-linked Ara h 2 (RC-Ara h 2) induced lower sensitization in mice, indicating its lower allergenicity. Reduction and MTGase-catalyzed cross-linking are effective methods to decrease the allergenicity of Ara h 2. The reactions involved linear allergen epitopes destroying the material basis of the allergenicity, and this might develop a new direction for protein desensitization processes.

Roles of the Lewis acid and base in the chemical reduction of CO2 catalyzed by frustrated Lewis pairs.

PubMed

Lim, Chern-Hooi; Holder, Aaron M; Hynes, James T; Musgrave, Charles B

2013-09-03

We employ quantum chemical calculations to discover how frustrated Lewis pairs (FLP) catalyze the reduction of CO2 by ammonia borane (AB); specifically, we examine how the Lewis acid (LA) and Lewis base (LB) of an FLP activate CO2 for reduction. We find that the LA (trichloroaluminum, AlCl3) alone catalyzes hydride transfer (HT) to CO2 while the LB (trimesitylenephosphine, PMes3) actually hinders HT; inclusion of the LB increases the HT barrier by ∼8 kcal/mol relative to the reaction catalyzed by LAs only. The LB hinders HT by donating its lone pair to the LUMO of CO2, increasing the electron density on the C atom and thus lowering its hydride affinity. Although the LB hinders HT, it nonetheless plays a crucial role by stabilizing the active FLP·CO2 complex relative to the LA dimer, free CO2, and free LB. This greatly increases the concentration of the reactive complex in the form FLP·CO2 and thus increases the rate of reaction. We expect that the principles we describe will aid in understanding other catalytic CO2 reductions.

Acid-catalyzed dehydrogenation of amine-boranes

DOEpatents

Stephens, Frances Helen; Baker, Ralph Thomas

2010-01-12

A method of dehydrogenating an amine-borane using an acid-catalyzed reaction. The method generates hydrogen and produces a solid polymeric [R.sup.1R.sup.2B--NR.sup.3R.sup.4].sub.n product. The method of dehydrogenating amine-boranes may be used to generate H.sub.2 for portable power sources.

Cytidine Diphosphoramidate Kinase: An Enzyme Required for the Biosynthesis of the O-Methyl Phosphoramidate Modification in the Capsular Polysaccharides of Campylobacter jejuni.

PubMed

Taylor, Zane W; Raushel, Frank M

2018-04-17

Campylobacter jejuni, a leading cause of gastroenteritis, produces a capsular polysaccharide that is derivatized with a unique O-methyl phosphoramidate (MeOPN) modification. This modification contributes to serum resistance and invasion of epithelial cells. Previously, the first three biosynthetic steps for the formation of MeOPN were elucidated. The first step is catalyzed by a novel glutamine kinase (Cj1418), which catalyzes the adenosine triphosphate (ATP)-dependent phosphorylation of the amide nitrogen of l-glutamine. l-Glutamine phosphate is used by cytidine triphosphate (CTP):phosphoglutamine cytidylyltransferase (Cj1416) to displace pyrophosphate from CTP to generate cytidine diphosphate (CDP)-l-glutamine, which is then hydrolyzed by γ-glutamyl-CDP-amidate hydrolase (Cj1417) to form cytidine diphosphoramidate (CDP-NH 2 ). Here, we show that Cj1415 catalyzes the ATP-dependent phosphorylation of CDP-NH 2 to form 3'-phospho-cytidine-5'-diphosphoramidate. Cj1415 will also catalyze the phosphorylation of adenosine diphosphoramidate (ADP-NH 2 ) and uridine diphosphoramidate (UDP-NH 2 ) but at significantly reduced rates. It is proposed that Cj1415 be named cytidine diphosphoramidate kinase.

Mechanism of intermolecular hydroacylation of vinylsilanes catalyzed by a rhodium(I) olefin complex: a DFT study.

PubMed

Meng, Qingxi; Shen, Wei; Li, Ming

2012-03-01

Density functional theory (DFT) was used to investigate the Rh(I)-catalyzed intermolecular hydroacylation of vinylsilane with benzaldehyde. All intermediates and transition states were optimized completely at the B3LYP/6-31G(d,p) level (LANL2DZ(f) for Rh). Calculations indicated that Rh(I)-catalyzed intermolecular hydroacylation is exergonic, and the total free energy released is -110 kJ mol(-1). Rh(I)-catalyzed intermolecular hydroacylation mainly involves the active catalyst CA2, rhodium-alkene-benzaldehyde complex M1, rhodium-alkene-hydrogen-acyl complex M2, rhodium-alkyl-acyl complex M3, rhodium-alkyl-carbonyl-phenyl complex M4, rhodium-acyl-phenyl complex M5, and rhodium-ketone complex M6. The reaction pathway CA2 + R2 → M1b → T1b → M2b → T2b1 → M3b1 → T4b → M4b → T5b → M5b → T6b → M6b → P2 is the most favorable among all reaction channels of Rh(I)-catalyzed intermolecular hydroacylation. The reductive elimination reaction is the rate-determining step for this pathway, and the dominant product predicted theoretically is the linear ketone, which is consistent with Brookhart's experiments. Solvation has a significant effect, and it greatly decreases the free energies of all species. The use of the ligand Cp' (Cp' = C(5)Me(4)CF(3)) decreased the free energies in general, and in this case the rate-determining step was again the reductive elimination reaction.

The effect of Mg/2+/ and Ca/2+/ on urea-catalyzed phosphorylation reactions

NASA Technical Reports Server (NTRS)

Handschuk, G. J.; Lohrmann, R.; Orgel, L. E.

1973-01-01

The effect of Mg(2+) and Ca(2+) on phosphorylation reactions catalyzed by urea is investigated, showing that Mg(2+) improves markedly the yield of products containing pyrophosphate bonds. Yields of up to 25% of uridine diphosphate can be obtained with struvite at temperatures as low as 65 C.

Rhodium(III)-Catalyzed [3+2]/[5+2] Annulation of 4-Aryl 1,2,3-Triazoles with Internal Alkynes through Dual C(sp2)-H Functionalization.

PubMed

Yang, Yuan; Zhou, Ming-Bo; Ouyang, Xuan-Hui; Pi, Rui; Song, Ren-Jie; Li, Jin-Heng

2015-05-26

A rhodium(III)-catalyzed [3+2]/[5+2] annulation of 4-aryl 1-tosyl-1,2,3-triazoles with internal alkynes is presented. This transformation provides straightforward access to indeno[1,7-cd]azepine architectures through a sequence involving the formation of a rhodium(III) azavinyl carbene, dual C(sp(2))-H functionalization, and [3+2]/[5+2] annulation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of aza-fused polycyclic quinolines through copper-catalyzed cascade reactions.

PubMed

Cai, Qian; Li, Zhengqiu; Wei, Jiajia; Fu, Liangbin; Ha, Chengyong; Pei, Duanqing; Ding, Ke

2010-04-02

A new and efficient method for the synthesis of aza-fused polycyclic quinolines (e.g., benzimidazo[1,2-a]quinolines) is described. This protocol includes an intermolecular condensation followed by a copper-catalyzed intramolecular C-N coupling reaction. The method is applied to a wide range of 2-iodo, 2-bromo, and 2-chloro aryl aldehyde substrates to yield the aza-fused polycyclic quinolines in good yields.

Autoinduced catalysis and inverse equilibrium isotope effect in the frustrated Lewis pair catalyzed hydrogenation of imines.

PubMed

Tussing, Sebastian; Greb, Lutz; Tamke, Sergej; Schirmer, Birgitta; Muhle-Goll, Claudia; Luy, Burkhard; Paradies, Jan

2015-05-26

The frustrated Lewis pair (FLP)-catalyzed hydrogenation and deuteration of N-benzylidene-tert-butylamine (2) was kinetically investigated by using the three boranes B(C6F5)3 (1), B(2,4,6-F3-C6H2)3 (4), and B(2,6-F2-C6H3)3 (5) and the free activation energies for the H2 activation by FLP were determined. Reactions catalyzed by the weaker Lewis acids 4 and 5 displayed autoinductive catalysis arising from a higher free activation energy (2 kcal mol(-1)) for the H2 activation by the imine compared to the amine. Surprisingly, the imine reduction using D2 proceeded with higher rates. This phenomenon is unprecedented for FLP and resulted from a primary inverse equilibrium isotope effect. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly Sensitive H2S Sensor Based on the Metal-Catalyzed SnO2 Nanocolumns Fabricated by Glancing Angle Deposition

PubMed Central

Yoo, Kwang Soo; Han, Soo Deok; Moon, Hi Gyu; Yoon, Seok-Jin; Kang, Chong-Yun

2015-01-01

As highly sensitive H2S gas sensors, Au- and Ag-catalyzed SnO2 thin films with morphology-controlled nanostructures were fabricated by using e-beam evaporation in combination with the glancing angle deposition (GAD) technique. After annealing at 500 °C for 40 h, the sensors showed a polycrystalline phase with a porous, tilted columnar nanostructure. The gas sensitivities (S = Rgas/Rair) of Au and Ag-catalyzed SnO2 sensors fabricated by the GAD process were 0.009 and 0.015, respectively, under 5 ppm H2S at 300 °C, and the 90% response time was approximately 5 s. These sensors showed excellent sensitivities compared with the SnO2 thin film sensors that were deposited normally (glancing angle = 0°, S = 0.48). PMID:26134105

Palladium-Catalyzed Asymmetric Allylic Alkylation of 4-Substituted Isoxazolidin-5-ones: Straightforward Access to β2,2 -Amino Acids.

PubMed

Nascimento de Oliveira, Marllon; Arseniyadis, Stellios; Cossy, Janine

2018-04-03

We report here an unprecedented and highly enantioselective palladium-catalyzed allylic alkylation applied to 4-substituted isoxazolidin-5-ones. Ultimately, the process provides a straightforward access to β 2,2 -amino acids bearing an all-carbon quaternary stereogenic center in great yields and a high degree of enantioselectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalyzed Atomic Layer Deposition of Silicon Oxide at Ultralow Temperature Using Alkylamine.

PubMed

Mayangsari, Tirta R; Park, Jae-Min; Yusup, Luchana L; Gu, Jiyeon; Yoo, Jin-Hyuk; Kim, Heon-Do; Lee, Won-Jun

2018-06-12

We report the catalyzed atomic layer deposition (ALD) of silicon oxide using Si 2 Cl 6 , H 2 O, and various alkylamines. The density functional theory (DFT) calculations using the periodic slab model of the SiO 2 surface were performed for the selection of alternative Lewis base catalysts with high catalytic activities. During the first half-reaction, the catalysts with less steric hindrance such as pyridine would be more effective than bulky alkylamines despite lower nucleophilicity. On the other hand, during the second half-reaction, the catalysts with a high nucleophilicity such as triethylamine (Et 3 N) would be more efficient because the steric hindrance is less critical. The in situ process monitoring shows that the calculated atomic charge is a good indicator for expecting the catalyst activity in the ALD reaction. The use of Et 3 N in the second half-reaction was essential to improving the growth rate as well as the step coverage of the film because the Et 3 N-catalyzed process deposited a SiO 2 film with a step coverage of 98% that is better than 93% of the pyridine-catalyzed process. The adsorption of pyridine, ammonia (NH 3 ), or trimethylamine (Me 3 N) salts was more favorable than that of Et 3 N, n-Pr 3 N, or i Pr 3 N salts. Therefore, Et 3 N was expected to incorporate less amine salts in the film as compared to pyridine, and the compositional analyses confirmed that the concentrations of Cl and N by the Et 3 N-catalyzed process were significantly lower than those by the pyridine-catalyzed process.

Susceptibility of Goethite to Fe2+-Catalyzed Recrystallization over Time.

PubMed

Joshi, Prachi; Fantle, Matthew S; Larese-Casanova, Philip; Gorski, Christopher A

2017-10-17

Recent work has shown that iron oxides, such as goethite and hematite, may recrystallize in the presence of aqueous Fe 2+ under anoxic conditions. This process, referred to as Fe 2+ -catalyzed recrystallization, can influence water quality by causing the incorporation/release of environmental contaminants and biological nutrients. Accounting for the effects of Fe 2+ -catalyzed recrystallization on water quality requires knowing the time scale over which recrystallization occurs. Here, we tested the hypothesis that nanoparticulate goethite becomes less susceptible to Fe 2+ -catalyzed recrystallization over time. We set up two batches of reactors in which 55 Fe 2+ tracer was added at two different time points and tracked the 55 Fe partitioning in the aqueous and goethite phases over 60 days. Less 55 Fe uptake occurred between 30 and 60 days than between 0 and 30 days, suggesting goethite recrystallization slowed with time. Fitting the data with a box model indicated that 17% of the goethite recrystallized after 30 days of reaction, and an additional 2% recrystallized between 30 and 60 days. The decreasing susceptibility of goethite to recrystallize as it reacted with aqueous Fe 2+ suggested that recrystallization is likely only an important process over short time scales.

Gas Pressure Monitored Iodide-Catalyzed Decomposition Kinetics of H[subscript 2]O[subscript 2]: Initial-Rate and Integrated-Rate Methods in the General Chemistry Lab

ERIC Educational Resources Information Center

Nyasulu, Frazier; Barlag, Rebecca

2010-01-01

The reaction kinetics of the iodide-catalyzed decomposition of [subscript 2]O[subscript 2] using the integrated-rate method is described. The method is based on the measurement of the total gas pressure using a datalogger and pressure sensor. This is a modification of a previously reported experiment based on the initial-rate approach. (Contains 2…

MINERALIZATION OF A SORBED POLYCYCLIC AROMATIC HYDROCARBON IN TWO SOILS USING CATALYZED HYDROGEN PEROXIDE. (R826163)

EPA Science Inventory

Hydrogen peroxide (H₂O₂) catalyzed by soluble iron or naturally occurring soil minerals, (i.e., modified Fenton's reagent) was investigated as a basis for mineralizing sorbed and NAPL-phase benzo[a]pyrene (BaP), a hydrophobic and toxic polycyclic a...

Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.

Pd/C catalyzes C-O bond cleavage of aryl ethers (diphenyl ether and cyclohexyl phenyl ether) by methanol in H2. The aromatic C-O bond is cleaved by reductive methanolysis, which is initiated by Pd-catalyzed partial hydrogenation of one phenyl ring to form an enol ether. The enol ether reacts rapidly with methanol to form a ketal, which generates methoxycyclohexene by eliminating phenol or an alkanol. Subsequent hydrogenation leads to methoxycyclohexane.

Quantum chemical studies of a model for peptide bond formation. 3. Role of magnesium cation in formation of amide and water from ammonia and glycine

NASA Technical Reports Server (NTRS)

Oie, T.; Loew, G. H.; Burt, S. K.; MacElroy, R. D.

1984-01-01

The SN2 reaction between glycine and ammonia molecules with magnesium cation Mg2+ as a catalyst has been studied as a model reaction for Mg(2+)-catalyzed peptide bond formation using the ab initio Hartree-Fock molecular orbital method. As in previous studies of the uncatalyzed and amine-catalyzed reactions between glycine and ammonia, two reaction mechanisms have been examined, i.e., a two-step and a concerted reaction. The stationary points of each reaction including intermediate and transition states have been identified and free energies calculated for all geometry-optimized reaction species to determine the thermodynamics and kinetics of each reaction. Substantial decreases in free energies of activation were found for both reaction mechanisms in the Mg(2+)-catalyzed amide bond formation compared with those in the uncatalyzed and amine-catalyzed amide bond formation. The catalytic effect of the Mg2+ cation is to stabilize both the transition states and intermediate, and it is attributed to the neutralization of the developing negative charge on the electrophile and formation of a conformationally flexible nonplanar five-membered chelate ring structure.

Investigation of the growth and in situ heating transmission electron microscopy analysis of Ag2S-catalyzed ZnS nanowires

NASA Astrophysics Data System (ADS)

Kim, Jung Han; Kim, Jong Gu; Song, Junghyun; Bae, Tae-Sung; Kim, Kyou-Hyun; Lee, Young-Seak; Pang, Yoonsoo; Oh, Kyu Hwan; Chung, Hee-Suk

2018-04-01

We investigated the semiconductor-catalyzed formation of semiconductor nanowires (NWs) - silver sulfide (Ag2S)-catalyzed zinc sulfide (ZnS) NWs - based on a vapor-liquid-solid (VLS) growth mechanism through metal-organic chemical vapor deposition (MOCVD) with a Ag thin film. The Ag2S-catalyzed ZnS NWs were confirmed to have a wurtzite structure with a width and length in the range of ∼30 nm to ∼80 nm and ∼1 μm, respectively. Using extensive transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) analyses from plane and cross-sectional viewpoints, the ZnS NWs were determined to have a c-axis, [0001] growth direction. In addition, the catalyst at the top of the ZnS NWs was determined to consist of a Ag2S phase. To support the Ag2S-catalyzed growth of the ZnS NWs by a VLS reaction, an in situ heating TEM experiment was conducted from room temperature to 840 °C. During the experiment, the melting of the Ag2S catalyst in the direction of the ZnS NWs was first observed at approximately 480 °C along with the formation of a carbon (C) shell. Subsequently, the Ag2S catalyst melted completely into the ZnS NWs at approximately 825 °C. As the temperature further increased, the Ag2S and ZnS NWs continuously melted and vaporized up to 840 °C, leaving only the C shell behind. Finally, a possible growth mechanism was proposed based on the structural and chemical investigations.

Palladium-catalyzed double carbonylation using near stoichiometric carbon monoxide: expedient access to substituted 13C2-labeled phenethylamines.

PubMed

Nielsen, Dennis U; Neumann, Karoline; Taaning, Rolf H; Lindhardt, Anders T; Modvig, Amalie; Skrydstrup, Troels

2012-07-20

A novel and general approach for (13)C(2)- and (2)H-labeled phenethylamine derivatives has been developed, based on a highly convergent single-step assembly of the carbon skeleton. The efficient incorporation of two carbon-13 isotopes into phenethylamines was accomplished using a palladium-catalyzed double carbonylation of aryl iodides with near stoichiometric carbon monoxide.

Glycerol Dehydration to Acrolein Catalyzed by ZSM-5 Zeolite in Supercritical Carbon Dioxide Medium.

PubMed

Zou, Bin; Ren, Shoujie; Ye, X Philip

2016-12-08

Supercritical carbon dioxide (SC-CO 2 ) has been used for the first time as a reaction medium for the dehydration of glycerol to acrolein catalyzed by a solid acid. Unprecedented catalyst stability over 528 hours of time-on-stream was achieved and the rate of coke deposition on the zeolite catalyst was the lowest among extensive previous studies, showing potential for industrial application. Coking pathways in SC-CO 2 were also elucidated for future development. The results have potential implications for other dehydration reactions catalyzed by solid acids. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

First Novozym 435 lipase-catalyzed Morita-Baylis-Hillman reaction in the presence of amides.

PubMed

Tian, Xuemei; Zhang, Suoqin; Zheng, Liangyu

2016-03-01

The first Novozym 435 lipase-catalyzed Morita-Baylis-Hillman (MBH) reaction with amides as co-catalyst was realized. Results showed that neither Novozym 435 nor amide can independently catalyze the reaction. This co-catalytic system that used a catalytic amount of Novozym 435 with a corresponding amount of amide was established and optimized. The MBH reaction strongly depended on the structure of aldehyde substrate, amide co-catalyst, and reaction additives. The optimized reaction yield (43.4%) was achieved in the Novozym 435-catalyzed MBH reaction of 2, 4-dinitrobenzaldehyde and cyclohexenone with isonicotinamide as co-catalyst and β-cyclodextrin as additive only in 2 days. Although enantioselectivity of Novozym 435 was not found, the results were still significant because an MBH reaction using lipase as biocatalyst was realized for the first time. Copyright © 2015 Elsevier Inc. All rights reserved.

Regioselective, borinic acid-catalyzed monoacylation, sulfonylation and alkylation of diols and carbohydrates: expansion of substrate scope and mechanistic studies.

PubMed

Lee, Doris; Williamson, Caitlin L; Chan, Lina; Taylor, Mark S

2012-05-16

Synthetic and mechanistic aspects of the diarylborinic acid-catalyzed regioselective monofunctionalization of 1,2- and 1,3-diols are presented. Diarylborinic acid catalysis is shown to be an efficient and general method for monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups (7 examples, 88% average yield). In addition, the scope of the selective acylation, sulfonylation, and alkylation is extended to 1,2- and 1,3-diols not derived from carbohydrates (28 examples); the efficiency, generality, and operational simplicity of this method are competitive with those of state-of-the-art protocols including the broadly applied organotin-catalyzed or -mediated reactions. Mechanistic details of the organoboron-catalyzed processes are explored using competition experiments, kinetics, and catalyst structure-activity relationships. These experiments are consistent with a mechanism in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.

Pd-catalyzed one-pot synthesis of polysubstituted acrylamidines from isocyanides, diazo compounds, and imines.

PubMed

Yan, Xu; Liao, Jinxi; Lu, Yongzhi; Liu, Jinsong; Zeng, Youlin; Cai, Qian

2013-05-17

A novel and efficient Pd-catalyzed one-pot reaction of ethyl diazoacetate, isocyanides, and imines for the synthesis of acrylamidines was developed. The multicomponent reaction may have occurred through an unpredicted ring-opening process of the ketenimine-imine [2 + 2] intermediate to form the acrylamidine products.

Rhodium(III)-catalyzed vinylic sp2 C-H bond functionalization: efficient synthesis of pyrido[1,2-α]benzimidazoles and imidazo[1,2-α]pyridines.

PubMed

Dong, Lin; Huang, Ji-Rong; Qu, Chuan-Hua; Zhang, Qian-Ru; Zhang, Wei; Han, Bo; Peng, Cheng

2013-09-28

A simple approach for synthesis of novel aza-fused scaffolds such as pyrido[1,2-α]benzimidazoles and imidazo[1,2-α]pyridines was developed by Rh(III)-catalyzed direct oxidative coupling between alkenes and unactivated alkynes without an extra directing group. The method would allow a broad substrate scope, providing fused heterocycles with potential biological properties.

Kinetic Behavior of Exchange-Driven Growth with Catalyzed-Birth Processes

NASA Astrophysics Data System (ADS)

Wang, Hai-Feng; Lin, Zhen-Quan; Kong, Xiang-Mu

2006-12-01

Two catalyzed-birth models of n-species (n>=2) aggregates with exchange-driven growth processes are proposed and compared. In the first one, the exchange reaction occurs between any two aggregates Amk and Amj of the same species with the rate kernels Km(k,j) = Kmkj (m = 1,2,...,n, n>=2), and aggregates of An species catalyze a monomer-birth of Al species (l = 1,2,...,n-1) with the catalysis rate kernel Jl(k,j) = Jlkjυ. The kinetic behaviors are investigated by means of the mean-field theory. We find that the evolution behavior of aggregate-size distribution alk(t) of Al species depends crucially on the value of the catalysis rate parameter υ: (i) alk(t) obeys the conventional scaling law in the case of υ<=0, (ii) alk(t) satisfies a modified scaling form in the case of υ>0. In the second model, the mechanism of monomer-birth of An-species catalyzed by Al species is added on the basis of the first model, that is, the aggregates of Al and An species catalyze each other to cause monomer-birth. The kinetic behaviors of Al and An species are found to fall into two categories for the different υ: (i) growth obeying conventional scaling form with υ<=0, (ii) gelling at finite time with υ>0.

Copper-catalyzed C(sp3)-OH cleavage with concomitant C-C coupling: synthesis of 3-substituted isoindolinones.

PubMed

Rao, H Surya Prakash; Rao, A Veera Bhadra

2015-02-06

Copper(II) trifluoromethanesulfonate (Cu(OTf)2) efficiently catalyzes the C-C coupling of 3-hydoxyisoindolinones with a variety of aryl-, heteroaryl-, and alkenylboronic acids to furnish C(3) aryl-, heteroaryl-, and alkenyl-substituted isoindolinones. The coupling reactions work smoothly in 1,2-dicholoroethane (DCE) reflux, to effect both inter- and intramolecular versions. This is the first report on C(sp(3))-OH cleavage with concomitant C-C coupling. The photolabile 2-nitrobenzyl protecting group is most appropriate for promotion of the coupling reaction and for deprotection. The tetracyclic ring motif of the alkaloid neuvamine was prepared by applying the newly developed copper-catalyzed C-C coupling.

Treatment Of Polychlorinated Biphenyls In Two Surface Soils Using Catalyzed H2O2 Propagations

EPA Science Inventory

Two surface soils contaminated with polychlorinated biphenyls (PCBs) collected from Superfund sites in the New England region of the United States, Fletcher Paints and Merrimack Industrial Metals, were evaluated for field treatment at the bench level using catalyzed H₂...

A recyclable palladium-catalyzed synthesis of 2-methylene-2,3-dihydrobenzofuran-3-ols by cycloisomerization of 2-(1-hydroxyprop-2-ynyl)phenols in ionic liquids.

PubMed

Mancuso, Raffaella; Gabriele, Bartolo

2013-09-04

A recyclable palladium-catalyzed synthesis of 2-methylene-2,3-dihydrobenzofuran-3-ols 2 by heterocyclization of 2-(1-hydroxyprop-2-ynyl)phenols 1 in an ionic liquid medium (BmimBF4) is presented. The process takes place under relatively mild conditions (100 °C, 5 h) in the presence of catalytic amounts (2 mol %) of PdI2 in conjunction with KI (5 equiv with respect to PdI2) and an organic base, such as morpholine (1 equiv with respect to 1), to give 2 in high yields (70%-86%). The PdI2-KI catalytic system could be recycled up to six times without appreciable loss of activity. Moreover, products 2 could be easily converted in a one-pot fashion into 2-hydroxymethylbenzofurans 3 (52%-71%, based on 1) and 2-methoxymethylbenzofurans 4 (52%-80%, based on 1) by acid-catalyzed allylic isomerization or allylic nucleophilic substitution.

Acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicyclo[2.2.1]hept-5-ene with alcohols.

PubMed

Tait, Katrina; Horvath, Alysia; Blanchard, Nicolas; Tam, William

2017-01-01

The acid-catalyzed ring-opening reactions of a cyclopropanated 3-aza-2-oxabicylic alkene using alcohol nucleophiles were investigated. Although this acid-catalyzed ring-opening reaction did not cleave the cyclopropane unit as planned, this represent the first examples of ring-openings of cyclopropanated 3-aza-2-oxabicyclo[2.2.1]alkenes that lead to the cleavage of the C-O bond instead of the N-O bond. Different acid catalysts were tested and it was found that pyridinium toluenesulfonate in methanol gave the best yields in the ring-opening reactions. The scope of the reaction was successfully expanded to include primary, secondary, and tertiary alcohol nucleophiles. Through X-ray crystallography, the stereochemistry of the product was determined which confirmed an S N 2-like mechanism to form the ring-opened product.

Facile Iodine-Catalyzed Michael Addition of Indoles to α,α′-Bis(arylmethylene)cyclopentanones: An Efficient Synthesis of E-2-(3-Indolylphenylmethyl)-5-phenylmethylenecyclopentanones

PubMed Central

Pal, Rammohan; Das Gupta, Arpita; Mallik, Asok K.

2012-01-01

Iodine-catalyzed reaction of indoles with α,α′-bis(arylmethylene)cyclopentanones afforded one diastereomer of the corresponding Michael adducts, namely, E-2-(3-indolylphenylmethyl)-5-phenylmethylenecyclopentanones, in a good yield. The products form a new group of indole derivatives. PMID:24052849

Synthesis of isocoumarins through three-component couplings of arynes, terminal alkynes, and carbon dioxide catalyzed by an NHC-copper complex.

PubMed

Yoo, Woo-Jin; Nguyen, Thanh V Q; Kobayashi, Shū

2014-09-15

A copper-catalyzed multicomponent coupling reaction between in situ generated ortho-arynes, terminal alkynes, and carbon dioxide was developed to access isocoumarins in moderate to good yields. The key to this CO2-incorporating reaction was the use of a versatile N-heterocyclic carbene/copper complex that was able to catalyze multiple transformations within the three-component reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biocatalytic synthesis of maltodextrin-based acrylates from starch and α-cyclodextrin.

PubMed

Kloosterman, Wouter M J; Spoelstra-van Dijk, Gerda; Loos, Katja

2014-09-01

Novel 2-(β-maltooligooxy)-ethyl (meth)acrylate monomers are successfully synthesized by CGTase from Bacillus macerans catalyzed coupling of 2-(β-glucosyloxy)-ethyl acrylate and methacrylate with α-cyclodextrin or starch. HPLC-UV analysis shows that the CGTase catalyzed reaction yields 2-(β-maltooligooxy)-ethyl acrylates with 1 to 15 glucopyranosyl units. (1) H NMR spectroscopy reveals that the β-linkage in the acceptor molecule is preserved during the CGTase catalyzed coupling reaction, whereas the newly introduced glucose units are attached by α-(1,4)-glycosidic linkages. The synthesized 2-(β-maltooligooxy)-ethyl acrylate monomers are successfully polymerized by aqueous free radical polymerization to yield the comb-shaped glycopolymer poly(2-(β-maltooligooxy)-ethyl acrylate). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wash Bottle Laboratory Exercises: Iodide-Catalyzed H[subscript 2]O[subscript 2] Decomposition Reaction Kinetics Using the Initial Rate Approach

ERIC Educational Resources Information Center

Barlag, Rebecca; Nyasulu, Frazier

2010-01-01

A wash bottle water displacement scheme is used to determine the kinetics of the iodide-catalyzed H[subscript 2]O[subscript 2] decomposition reaction. The reagents (total volume 5.00 mL) are added to a test tube that is placed in a wash bottle containing water. The mass of the water displaced in [approximately]60 s is measured. The reaction is…

OXALOACETATE DECARBOXYLATION AND OXALOACETATE-CARBON DIOXIDE EXCHANGE IN ACETOBACTER XYLINUM

PubMed Central

Benziman, Moshe; Heller, N.

1964-01-01

Benziman, Moshe (The Hebrew University of Jerusalem, Jerusalem, Israel), and N. Heller. Oxaloacetate decarboxylation and oxaloacetate-carbon dioxide exchange in Acetobacter xylinum. J. Bacteriol. 88:1678–1687. 1964.—Extracts of Acetobacter xylinum, prepared by sonic treatment, were shown to catalyze the decarboxylation of oxaloacetate (OAA) to pyruvate and CO2, and the exchange of C14-carbon dioxide into the β-carboxyl of OAA. Fractionation of the extracts with ammonium sulfate resulted in a 10-fold increase of the specific activity of the enzyme system catalyzing the CO2 exchange and OAA decarboxylation reactions. The purified preparation catalyzed the exchange of pyruvate-3-C14 into OAA. Similar pH curves with a pH optimum of 5.6 were obtained for the CO2 exchange and OAA decarboxylation reactions. Both reactions require the presence of Mn2+ or Mg2+ ions. OAA decarboxylation was more strongly inhibited than the exchange of CO2 by dialysis or metal-chelating agents. Avidin did not inhibit either reaction. Adenosine triphosphate (ATP), adenosine diphosphate (ADP), guanosine triphosphate (GTP), guanosine diphosphate (GDP), pyrophosphate, or inorganic phosphate did not promote OAA decarboxylation and the CO2-exchange reaction catalyzed by the purified preparation. The purified preparation failed to catalyze the carboxylation of phosphoenolpyruvate in the presence of GDP, ADP, or inorganic phosphate, and that of pyruvate in the presence of ATP or GTP, even when supplemented with an OAA-trapping system. A scheme for OAA decarboxylation which could account for the observed exchange reactions and for the failure to obtain net fixation of CO2 is proposed. The relation between the exchange reaction and the synthesis of cellulose from pyruvate by A. xylinum is discussed. PMID:14240957

Acid-catalyzed rearrangements of flavan-4-phloroglucinol derivatives to novel 6-hydroxyphenyl-6a,llb-dihydro-6H-[1]benzofuro[2,3-c]-chromenes and hydroxyphenyl-3,2'-spirobi[dihydro[l]benzofurans

Treesearch

Petrus J. Steynberg; Jan P. Steynberg; Richard W. Hemingway; Daneel Ferreira; G. Wayne McGraw

1997-01-01

Acetic acid-catalyzed cleavage of proanthocyanidins in the presence of phloroglucinol gives a series of 2R procyanidin- and prodelphinidin-phloroglucinol adducts together with a novel 2S all-cis derivative implicating cleavage of the pyran ring and subsequent inversion of stereochernistry at C-2c. These flavan-4-phloroglucinol adducts also suffer dehydration to...

Construction of Pyrrolo[1,2-a]indoles via Cobalt(III)-Catalyzed Enaminylation of 1-(Pyrimidin-2-yl)-1H-indoles with Ketenimines and Subsequent Base-Promoted Cyclization.

PubMed

Zhou, Xiaorong; Fan, Zili; Zhang, Zhiyin; Lu, Ping; Wang, Yanguang

2016-09-16

A cobalt(III)-catalyzed cross-coupling reaction of 1-(pyrimidin-2-yl)-1H-indoles with ketenimines is reported. The reaction provided 2-enaminylated indole derivatives in moderate to excellent yields with a broad substrate scope. The prepared 2-enaminylated indoles could be conveniently converted into pyrrolo[1,2-a]indoles, which are an important class of compounds in medicinal chemistry.

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

PubMed

Chen, Wenyong; Chen, Ming; Hartwig, John F

2014-11-12

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: Synergetic effect of ligands and barium enolates

DOE PAGES

Chen, Wenyong; Chen, Ming; Hartwig, John F.

2014-10-22

Here, we report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from ( R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

Co2(CO)8-catalyzed intramolecular hetero-Pauson-Khand reaction of alkynecarbodiimide: synthesis of (+/-)-physostigmine.

PubMed

Mukai, Chisato; Yoshida, Tatsunori; Sorimachi, Mao; Odani, Akira

2006-01-05

[reaction: see text] Herein we describe a novel Co(2)(CO)(8)-catalyzed intramolecular aza-Pauson-Khand-type reaction of alkynecarbodiimide derivatives affords pyrrolo[2,3-b]indol-2-one ring systems in reasonable yields. This is the first reported Co(2)(CO)(8) successfully applied in the hetero-Pauson-Khand reaction. Significantly, the transformation of one of our pyrrolo[2,3-b]indol-2-one derivatives into the indole alkaloid, (+/-)-physostigmine, was completed in a highly stereoselective manner.

Glymes as benign co-solvents for CaO-catalyzed transesterification of soybean oil to biodiesel.

PubMed

Tang, Shaokun; Zhao, Hua; Song, Zhiyan; Olubajo, Olarongbe

2013-07-01

The base (such as CaO)-catalyzed heterogeneous preparation of biodiesel encounters a number of obstacles including the need for CaO pretreatment and the reactions being incomplete (typically 90-95% yields). In this study, a number of glymes were investigated as benign solvents for the CaO-catalyzed transesterification of soybean oil into biodiesel with a high substrate loading (typically soybean oil >50% v/v). The triglyceride-dissolving capability of glymes led to a much faster reaction rate (>98% conversions in 4h) than in methanol alone (typically 24h) and minimized the saponification reaction when catalyzed by anhydrous CaO or commercial lime without pre-activation. The use of glyme (e.g. P2) as co-solvent also activates commercial lime to become an effective catalyst without calcination pretreatment. The SEM images suggest a dissolution-agglomeration process of CaO surface in the presence of P2, which could remove the CaCO3 and Ca(OH)2 layer coated on the surface of lime. Copyright © 2013 Elsevier Ltd. All rights reserved.

Biodegradation of p-nitrophenol via 1,2,4-benzenetriol by an Arthrobacter sp.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jain, R.K.; Spain, J.C.; Dreisbach, J.H.

1994-08-01

The degradation of p-nitrophenol (PNP) by Moraxella and Pseudomonas spp. involves an initial monooxygenase-catalyzed removal of the nitro group. The resultant hydroquinone is subject to ring fission catalyzed by a dioxygenase enzyme. A strain of an Arthrobacter sp. JS443, capable of degrading PNP with stoichiometric release of nitrite has been isolated. During induction of the enzymes required for growth on PNP, 1,2,4-benzenetriol was identified as an intermediate by gas chromatography-mass spectroscopy and radiotracer studies. 1,2,4-Benzenetriol was converted to maleylacetic acid, which was further degraded by the beta-ketoadipate pathway. Conversion of PNP to 1,2,4-benzenetriol is catalyzed by a monooxygenase system inmore » strain JS443 through the formation of 4-nitrocatechol, 4-nitroresorcinol, or both. Results clearly indicate the existence of an alternative pathway for the biodegradation of PNP. 15 refs, 2 figs., 2 tabs.« less

New insights into hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds by rhenium(V)-dioxo complexes.

PubMed

Huang, Liangfang; Wang, Wenmin; Wei, Xiaoqin; Wei, Haiyan

2015-04-23

The hydrosilylation of unsaturated carbon-heteroatom (C═O, C═N) bonds catalyzed by high-valent rhenium(V)-dioxo complex ReO2I(PPh3)2 (1) were studied computationally to determine the underlying mechanism. Our calculations revealed that the ionic outer-sphere pathway in which the organic substrate attacks the Si center in an η(1)-silane rhenium adduct to prompt the heterolytic cleavage of the Si-H bond is the most energetically favorable process for rhenium(V)-dioxo complex 1 catalyzed hydrosilylation of imines. The activation energy of the turnover-limiting step was calculated to be 22.8 kcal/mol with phenylmethanimine. This value is energetically more favorable than the [2 + 2] addition pathway by as much as 10.0 kcal/mol. Moreover, the ionic outer-sphere pathway competes with the [2 + 2] addition mechanism for rhenium(V)-dioxo complex 1 catalyzing the hydrosilylation of carbonyl compounds. Furthermore, the electron-donating group on the organic substrates would induce a better activity favoring the ionic outer-sphere mechanistic pathway. These findings highlight the unique features of high-valent transition-metal complexes as Lewis acids in activating the Si-H bond and catalyzing the reduction reactions.

Methoxy-Directed Aryl-to-Aryl 1,3-Rhodium Migration

PubMed Central

Zhang, Jing; Liu, Jun-Feng; Ugrinov, Angel; Pillai, Anthony F. X.; Sun, Zhong-Ming; Zhao, Pinjing

2015-01-01

Through-space metal/hydrogen shift is an important strategy for transition metal-catalyzed C-H bond activation. Here we describe the synthesis and characterization of a Rh(I) 2,6-dimethoxybenzoate complex that underwent stoichiometric rearrangement via a highly unusual 1,3- rhodium migration. This aryl-to-aryl 1,3-Rh/H shift was also demonstrated in a Rh(I)-catalyzed decarboxylative conjugate addition to form a C-C bond at a meta position instead of the ipso-carboxyl position. A deuterium-labeling study under the conditions of Rh(I)-catalyzed protodecarboxylation revealed the involvement of an ortho-methoxy group in a multi-step pathway of consecutive sp3 and sp2 C-H bond activations. PMID:24171626

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Ga and In modified ceria as supports for cobalt-catalyzed Fischer-Tropsch synthesis

DOE PAGES

Gnanamani, Muthu Kumaran; Jacobs, Gary; Shafer, Wilson D.; ...

2017-08-24

Ga- and In-modified ceria (Ce 0.8Ga 0.2O 2, Ce 0.8In 0.2O 2) materials were used as supports for cobalt-catalyzed Fischer-Tropsch synthesis (FTS). The addition of Ga to ceria was found to improve CO conversion for cobalt-catalyzed FTS, while the addition of In tended to decrease it. A similar trend was observed with the Ag-promoted cobalt/ceria catalysts. Doping of ceria with Ga or In decreased methane and increased the selectivity to olefins and alcohols for Ag-promoted cobalt/ceria. The sum of the products of olefins and alcohols for various catalysts exhibited a decreasing trend as follows: Ag-Co/Ce-Ga > Ag-Co/Ce-In > Ag-Co/Ce. Resultsmore » of H 2-TPR-XANES showed that adding of Ga or In to ceria increases the fraction of Ce 3+ in the surface shell for both unpromoted and Ag-promoted catalysts in the range of temperature typical of catalyst activation. In conclusion, this partially reduced ceria plays an important role in controlling the product selectivity of cobalt-catalyzed FT synthesis.« less

Rubber muscle actuation with pressurized CO2 from enzyme-catalyzed urea hydrolysis

NASA Astrophysics Data System (ADS)

Sutter, Thomas M.; Dickerson, Matthew B.; Creasy, Terry S.; Justice, Ryan S.

2013-09-01

A biologically inspired pneumatic pressure source was designed and sized to supply high pressure CO2(g) to power a rubber muscle actuator. The enzyme urease served to catalyze the hydrolysis of urea, producing CO2(g) that flowed into the actuator. The actuator’s power envelope was quantified by testing actuator response on a custom-built linear-motion rig. Reaction kinetics and available work density were determined by replacing the actuator with a double-action piston and measuring volumetric gas generation against a fixed pressure on the opposing piston. Under the conditions investigated, urease catalyzed the generation of up to 0.81 MPa (117 psi) of CO2(g) in the reactor headspace within 18 min, and the evolved gas produced a maximum work density of 0.65 J ml-1.

Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether.

PubMed

Evans, P Andrew; Leahy, David K

2003-07-30

The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare beta-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which alpha-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (-)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions.

Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.

PubMed

Li, Changkun; Kähny, Matthias; Breit, Bernhard

2014-12-08

A rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes to give branched N-allyl 2-pyridones is reported. Preliminary mechanistic studies support the hypothesis that the reaction was initiated from the more acidic 2-hydroxypyridine form, and the initial kinetic O-allylation product was finally converted into the thermodynamically more stable N-allyl 2-pyridones. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Au(I)-catalyzed rearrangement/cyclization cascade toward the synthesis of 2-substituted-1,4,5,6-tetrahydrocyclopenta[b]pyrrole.

PubMed

Mou, Xue-Qing; Xu, Zheng-Liang; Wang, Shao-Hua; Zhu, Dao-Yong; Wang, Jie; Bao, Wen; Zhou, Shi-Jiang; Yang, Chao; Zhang, Di

2015-08-04

An Au(I)-catalyzed tandem reaction for the synthesis of 2-phenyl-1,4,5,6-tetrahydrocyclopenta[b]pyrrole derivatives from 1-(1-hydroxy-3-phenylprop-2-yn-1-yl)cyclobutanol and primary amines or NH4OAc has been developed to afford a series of polysubstituted pyrroles in moderate to good yields.

Formate as a CO surrogate for cascade processes: Rh-catalyzed cooperative decarbonylation and asymmetric Pauson-Khand-type cyclization reactions.

PubMed

Lee, Hang Wai; Chan, Albert S C; Kwong, Fuk Yee

2007-07-07

A rhodium-(S)-xyl-BINAP complex-catalyzed tandem formate decarbonylation and [2 + 2 + 1] carbonylative cyclization is described; this cooperative process utilizes formate as a condensed CO source, and the newly developed cascade protocol can be extended to its enantioselective version, providing up to 94% ee of the cyclopentenone adducts.

Brønsted acid-catalyzed decarboxylative redox amination: formation of N-alkylindoles from azomethine ylides by isomerization.

PubMed

Mao, Hui; Wang, Sichang; Yu, Peng; Lv, Huiqing; Xu, Runsheng; Pan, Yuanjiang

2011-02-18

A Brønsted acid-catalyzed decarboxylative redox amination involving aldehydes with 2-carboxyindoline for the synthesis of N-alkylindoles is described. The decarboxylative condensations of aldehydes with 2-carboxyindoline produce azomethine ylides in situ, which then transform into N-alkylindoles by isomerization. © 2011 American Chemical Society

Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

PubMed

Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao

2016-03-04

A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.

Highly regioselective Lewis acid-catalyzed [3+2] cycloaddition of alkynes with donor-acceptor oxiranes by selective carbon-carbon bond cleavage of epoxides.

PubMed

Liu, Renrong; Zhang, Mei; Zhang, Junliang

2011-12-28

A novel, efficient, highly regioselective Sc(OTf)(3)-catalyzed [3+2] cycloaddition of electron-rich alkynes with donor-acceptor oxiranes via highly chemoselective C-C bond cleavage under mild conditions was developed. This journal is © The Royal Society of Chemistry 2011

Practical Iron- and Cobalt-Catalyzed Cross-Coupling Reactions between N-Heterocyclic Halides and Aryl or Heteroaryl Magnesium Reagents.

PubMed

Kuzmina, Olesya M; Steib, Andreas K; Fernandez, Sarah; Boudot, Willy; Markiewicz, John T; Knochel, Paul

2015-05-26

The reaction scope of iron- and cobalt-catalyzed cross-coupling reactions in the presence of isoquinoline (quinoline) in the solvent mixture tBuOMe/THF has been further investigated. Various 2-halogenated pyridine, pyrimidine, and triazine derivatives were arylated under these mild conditions in excellent yields. The presence of isoquinoline allows us to perform Fe-catalyzed cross-coupling reactions between 6-chloroquinoline and aryl magnesium reagents. Furthermore, it was found that the use of 10% N,N-dimethylquinoline-8-amine increases the yields of some Co-catalyzed cross-coupling reactions with chloropyridines bearing electron-withdrawing substituents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Suppression of BRCA2 by Mutant Mitochondrial DNA in Prostate Cancer

DTIC Science & Technology

2011-05-01

Briefly, the electron transfer activities of complex I/III (NADH dehydrogenase/cytochrome bc1 complex: catalyzes the electron transfer from NADH to...ferricytochrome c) and complex II/III (succinate dehydrogenase/cytochrome bc1 complex: catalyzes the electron transfer from succinate to ferricytochrome...The electron transfer activity of complex IV (cytochrome c oxidase: catalyzes the final step of the respiratory chain by transferring electrons from

Copper(II)-catalyzed oxidative [3+2] cycloaddition reactions of secondary amines with α-diazo compounds: a facile and efficient synthesis of 1,2,3-triazoles.

PubMed

Li, Yi-Jin; Li, Xue; Zhang, Shao-Xiao; Zhao, Yu-Long; Liu, Qun

2015-07-25

A novel copper-catalyzed [3+2] cycloaddition reaction of secondary amines with α-diazo compounds has been developed via a cross-dehydrogenative coupling process. The reaction involves a sequential aerobic oxidation/[3+2] cycloaddition/oxidative aromatization procedure and provides an efficient method for the construction of 1,2,3-triazoles in a single step in an atom-economic manner from readily available starting materials under very mild conditions.

Asymmetric synthesis of 5-arylcyclohexenones by rhodium(I)-catalyzed conjugate arylation of racemic 5-(trimethylsilyl)cyclohexenone with arylboronic acids.

PubMed

Chen, Qian; Kuriyama, Masami; Soeta, Takahiro; Hao, Xinyu; Yamada, Ken-ichi; Tomioka, Kiyoshi

2005-09-29

[reaction: see text] A catalytic asymmetric conjugate arylation of racemic 5-(trimethylsilyl)cyclohex-2-enone with arylboronic acids was catalyzed by 3 mol % chiral amidophosphane- or BINAP-Rh(I) in dioxane-water (10:1) to afford trans- and cis-3-aryl-5-(trimethylsilyl)cyclohexanones in high enantioselectivity. Dehydrosilylation of the product mixture with cupric chloride in DMF gave 5-arylcyclohex-2-enones with up to 93% ee in good yield. Enantiofacial selectivity with chiral phosphane-Rh(I) exceeds the trans-diastereoselectivity that is maintained in the achiral or racemic phosphane-Rh(I)-catalyzed conjugate arylation of 5-(trimethylsilyl)cyclohexenone.

Microwave-Assisted Synthesis of a Natural Insecticide on Basic Montmorillonite K10 Clay. Green Chemistry in the Undergraduate Organic Laboratory

ERIC Educational Resources Information Center

Dintzner, Matthew R.; Wucka, Paul R.; Lyons, Thomas W.

2006-01-01

A detailed investigation of the clay-catalyzed condensation of sesamol and other phenols with 3-methyl-2-butenal to give methylenedioxyprecocene (MDP) and other chromenes is presented. The clay-catalyzed microwave-assisted condensation of sesamol with 3-methyl-2-butenal is appropriate for incorporation into undergraduate organic laboratory…

Copper-catalyzed aerobic C(sp2)-H functionalization for C-N bond formation: synthesis of pyrazoles and indazoles.

PubMed

Li, Xianwei; He, Li; Chen, Huoji; Wu, Wanqing; Jiang, Huanfeng

2013-04-19

A simple, practical, and highly efficient synthesis of pyrazoles and indazoles via copper-catalyzed direct aerobic oxidative C(sp(2))-H amination has been reported herein. This process tolerated a variety of functional groups under mild conditions. Further diversification of pyrazoles was also investigated, which provided its potential for drug discovery.

Transition metal-catalyzed oxidation of atmospheric sulfur: Global implications for the sulfur budget

NASA Astrophysics Data System (ADS)

Alexander, Becky; Park, Rokjin J.; Jacob, Daniel J.; Gong, Sunling

2009-01-01

We use observations of the oxygen-17 excess (Δ17O) of sulfate in the Arctic to quantify the sulfate source from aqueous SO2 (S(IV)) oxidation by O2 catalyzed by transition metals. Due to the lack of photochemically produced OH and H2O2 in high latitudes during winter, combined with high anthropogenic SO2 emissions in the Northern Hemisphere, oxidation by O3 is predicted to dominate sulfate formation during winter in this region. However, Δ17O measurements of sulfate aerosol collected in Alert, Canada, are not consistent with O3 as the dominant oxidant and indicate that a S(IV) oxidant with near-zero Δ17O values (O2) is important during winter. We use a global chemical transport model to interpret quantitatively the Alert observations and assess the global importance of sulfate production by Fe(III)- and Mn(II)-catalyzed oxidation of S(IV) by O2. We scale anthropogenic and natural atmospheric metal concentrations to primary anthropogenic sulfate and dust concentrations, respectively. The solubility and oxidation state of these metals is determined by cloud liquid water content, source, and sunlight. By including metal-catalyzed S(IV) oxidation, the model is consistent with the Δ17O magnitudes in the Alert data during winter. Globally, we find that this mechanism contributes 9-17% to sulfate production. The inclusion of metal-catalyzed oxidation does not resolve model discrepancies with surface SO2 and sulfate observations in Europe. Oxygen isotope measurements of sulfate aerosols collected near anthropogenic and dust sources of metals would help to verify the importance of this sulfur oxidation pathway.

Spontaneous, Metal-Catalyzed, and Enzyme-Catalyzed Decarboxylation of Oxalosuccinic Acid.

DTIC Science & Technology

1980-01-01

acid, 2,4- dinitrophenylhydrazine was added. This yielded a hydrazone which, after two recrystallizations, melted at 2200C. A sample of the a...accurately determined to be 24,500 at a wavelength of 352 nm (46). 34 2,4- Dinitrophenylhydrazine . Obtained from the Eastman Kodak Chemicals Division...reaction with 2,4- dinitrophenylhydrazine (57). The reaction mixture was sampled hourly during the daytime for a period of three days. The concentration of a

Theoretical study on the reaction mechanisms of Michael chirality addition between propionaldehyde and nitroalkene catalyzed by an enantioselective catalyst.

PubMed

Zhou, Xinming; Li, Ling; Sun, Xuejun; Wang, Yajun; Du, Dongmei; Fu, Hui

2018-06-01

The asymmetric Michael addition between propionaldehyde and nitroalkene catalyzed by 8-(ethoxycarbonyl)-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid has obtained relatively high yields and excellent enantioselectivities at room temperature. In this study, the molecular structures and optical activity of the most stable conformation I are optimized at B3LYP/6-311++ G(d,p) level. We find that levorotatory conformation I catalyzing the same Michael addition can produce laevo-product A and dextrorotatory conformation I' can obtain the dextral-product A'. These results have guiding significance for further studying on the new chemzymes and the mechanism of the obtained different chiral products. © 2018 Wiley Periodicals, Inc.

Enzymatic synthesis of structured lipids.

PubMed

Iwasaki, Yugo; Yamane, Tsuneo

2004-01-01

Structured lipids (SLs) are defined as lipids that are modified chemically or enzymatically in order to change their structure. This review deals with structured triacylglycerols (STGs) and structured phospholipids (SPLs). The most typical STGs are MLM-type STGs, having medium chain fatty acids (FAs) at the 1- and 3-positions and a long chain fatty acid at the 2- position. MLM-type STGs are synthesized by: 1) 1,3-position-specific lipase-catalyzed acyl exchange of TG with FA or with FA ethylester (FAEt); 2) 1,3-position-specific lipase-catalyzed acylation of glycerol with FA, giving symmetric 1,3-diacyl-sn-glycerol, followed by chemical acylation at the sn-2 position, and; 3) 1,3-position-specific lipase-catalyzed deacylation of TG, giving 2-monoacylglycerol, followed by reacylation at the 1- and 3-positions with FA or with (FAEt). Enzymatic preparation of SPLs requires: 1) acyl group modification, and 2) head group modification of phospholipids. Acyl group modification is performed using lipases or phospholipase A2-mediated transesterification or ester synthesis to introduce arbitrary fatty acid to phospholipids. Head group modification is carried out by phospholipase D-catalyzed transphosphatidylation. A wide range of compounds can be introduced into the polar head of phospholipids, making it possible to prepare various SPLs.

Structural and stereoelectronic insights into oxygenase-catalyzed formation of ethylene from 2-oxoglutarate.

PubMed

Zhang, Zhihong; Smart, Tristan J; Choi, Hwanho; Hardy, Florence; Lohans, Christopher T; Abboud, Martine I; Richardson, Melodie S W; Paton, Robert S; McDonough, Michael A; Schofield, Christopher J

2017-05-02

Ethylene is important in industry and biological signaling. In plants, ethylene is produced by oxidation of 1-aminocyclopropane-1-carboxylic acid, as catalyzed by 1-aminocyclopropane-1-carboxylic acid oxidase. Bacteria catalyze ethylene production, but via the four-electron oxidation of 2-oxoglutarate to give ethylene in an arginine-dependent reaction. Crystallographic and biochemical studies on the Pseudomonas syringae ethylene-forming enzyme reveal a branched mechanism. In one branch, an apparently typical 2-oxoglutarate oxygenase reaction to give succinate, carbon dioxide, and sometimes pyrroline-5-carboxylate occurs. Alternatively, Grob-type oxidative fragmentation of a 2-oxoglutarate-derived intermediate occurs to give ethylene and carbon dioxide. Crystallographic and quantum chemical studies reveal that fragmentation to give ethylene is promoted by binding of l-arginine in a nonoxidized conformation and of 2-oxoglutarate in an unprecedented high-energy conformation that favors ethylene, relative to succinate formation.

Preparation of Benzo[c]carbazol-6-amines via Manganese-Catalyzed Enaminylation of 1-(Pyrimidin-2-yl)-1H-indoles with Ketenimines and Subsequent Oxidative Cyclization.

PubMed

Zhou, Xiaorong; Li, Zhenmin; Zhang, Zhiyin; Lu, Ping; Wang, Yanguang

2018-03-02

Manganese-catalyzed C 2 -H enaminylation of 1-(pyrimidin-2-yl)-1H-indoles with ketenimines is reported. The reaction provided 2-enaminylated indole derivatives in moderate to excellent yields with a broad substrate scope. A migration of the directing group pyrimidinyl occurred during this process. The synthesized 2-enaminyl indoles could be conveniently converted into 5-aryl-7H-benzo[c]carbazol-6-amines.

Multi-stage catalyst systems and uses thereof

DOEpatents

Ozkan, Umit S [Worthington, OH; Holmgreen, Erik M [Columbus, OH; Yung, Matthew M [Columbus, OH

2009-02-10

Catalyst systems and methods provide benefits in reducing the content of nitrogen oxides in a gaseous stream containing nitric oxide (NO), hydrocarbons, carbon monoxide (CO), and oxygen (O.sub.2). The catalyst system comprises an oxidation catalyst comprising a first metal supported on a first inorganic oxide for catalyzing the oxidation of NO to nitrogen dioxide (NO.sub.2), and a reduction catalyst comprising a second metal supported on a second inorganic oxide for catalyzing the reduction of NO.sub.2 to nitrogen (N.sub.2).

A proposed mechanism for Pt/SnO(x)-catalyzed CO oxidation

NASA Technical Reports Server (NTRS)

Schryer, David R.; Upchurch, Billy T.; Sidney, Barry D.; Brown, Kenneth G.; Hoflund, Gar B.; Herz, Richard K.

1991-01-01

A mechanism for Pt/SnO(x)-catalyzed CO oxidation is proposed, which is consistent with a broad range of experimental observations. CO oxidation catalysts with high activity at or near room temperature are used in closed-cycle CO2 lasers and air purification.

Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate.

PubMed

Hu, Yiwen; He, Qihui; Zhang, Zheng; Ding, Naidong; Hu, Baixing

2011-11-28

With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline.

Room-temperature Pd-catalyzed C-H chlorination by weak coordination: one-pot synthesis of 2-chlorophenols with excellent regioselectivity.

PubMed

Sun, Xiuyun; Sun, Yonghui; Zhang, Chao; Rao, Yu

2014-02-07

A room-temperature Pd(II)-catalyzed regioselective chlorination reaction has been developed for a facile one-pot synthesis of a broad range of 2-chlorophenols. The reaction demonstrates an excellent regioselectivity and reactivity for C-H chlorination. This reaction represents one of the rare examples of mild C-H functionalization at ambient temperature.

Construction of quaternary stereocenters: asymmetric α-amination of branched aldehydes catalyzed by monoimide substituted cyclohexane-1,2-diamines.

PubMed

Fu, Ji-Ya; Wang, Qi-Lin; Peng, Lin; Gui, Yong-Yuan; Xu, Xiao-Ying; Wang, Li-Xin

2013-10-01

A highly efficient enantioselective α-amination of branched aldehydes catalyzed by chiral imide monosubstituted 1,2-diamine derivatives was reported to afford the quaternary stereogenic centers in excellent yields (up to 99%) and enantioselectivities (up to 97% ee). Chirality 25:668-672, 2013. © 2013 Wiley Periodicals, Inc. © 2013 Wiley Periodicals, Inc.

A Highly Stereocontrolled, One-Pot Approach toward Pyrrolobenzoxazinones and Pyrroloquinazolinones through a Lewis Acid-Catalyzed [3 + 2]-Cycloannulation Process.

PubMed

Boomhoff, Michael; Ukis, Rostyslav; Schneider, Christoph

2015-08-21

We report herein a stereocontrolled [3 + 2]-cycloheteroannulation of bis-silyl dienediolate 1 with 2-aminobenzoic acid- and 2-aminobenzamide-derived imines to furnish highly substituted pyrrolo[1,2-a]benzoxazinones 3 and pyrrolo[1,2-a]quinazolinones 4, respectively, in good overall yields. This one-pot process rapidly generates molecular complexity and comprises a Lewis acid-catalyzed, vinylogous Mannich reaction of 1 followed by an intramolecular N,O-acetal- and N,N-aminal formation, respectively, which proceeds with good to excellent stereocontrol.

Gold-catalyzed sequential annulations towards 3,4-fused bi/tri-cyclic furans involving a [3+2+2]-cycloaddition.

PubMed

Liu, Suna; Yang, Pu; Peng, Shiyong; Zhu, Chenghao; Cao, Shengyu; Li, Jian; Sun, Jiangtao

2017-01-17

A gold-catalyzed sequential annulation reaction to prepare 3,4-fused bicyclic furan compounds has been realized by employing 2-(1-alkynyl)-2-alken-1-ones and 1,3,5-triazines as the starting materials under mild reaction conditions. This protocol features multiple bond formation in a single operation with the incorporation of two nitrogen and two carbon atoms into the final products. A mechanistic investigation reveals that the sequential annulations involved an unprecedented stepwise [3+2+2]-cycloaddition.

Indium-Catalyzed Reductive Dithioacetalization of Carboxylic Acids with Dithiols: Scope, Limitations, and Application to Oxidative Desulfurization.

PubMed

Nishino, Kota; Minato, Kohei; Miyazaki, Takahiro; Ogiwara, Yohei; Sakai, Norio

2017-04-07

In this study an InI 3 -TMDS (1,1,3,3-tetramethyldisiloxane) reducing system effectively catalyzed the reductive dithioacetalization of a variety of aromatic and aliphatic carboxylic acids with 1,2-ethanedithiol or 1,3-propanedithiol leading to the one-pot preparation of either 1,3-dithiolane derivatives or a 1,3-dithiane derivative. Also, the intact indium catalyst continuously catalyzed the subsequent oxidative desulfurization of an in situ formed 1,3-dithiolane derivative, which led to the preparation of the corresponding aldehydes.

Direct asymmetric aldol reaction of aryl ketones with aryl aldehydes catalyzed by chiral BINOL-derived zincate catalyst.

PubMed

Li, Hong; Da, Chao-Shan; Xiao, Yu-Hua; Li, Xiao; Su, Ya-Ning

2008-09-19

Direct asymmetric aldol reaction of aryl ketones with aryl aldehydes catalyzed by chiral metal complex is reported for the first time herein. Two novel semicrown chiral ligands 1a and 1b were synthesized from (S)- and (R)-BINOL, respectively, and then employed to catalyze the direct asymmetric aldol addition of aryl ketones to aryl aldehydes. Introduced with 2.0 equiv of diethylzinc, 1b had higher enantioselectivity than 1a. Up to 97% yield and up to 80% enantioselectivity were achieved.

Cobalt catalyzed carbonylation of unactivated C(sp3)–H bonds† †Electronic supplementary information (ESI) available. CCDC 1507203 (2t) & 1507204 (2a). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05026c Click here for additional data file. Click here for additional data file.

PubMed Central

Barsu, Nagaraju; Bolli, Shyam Kumar

2017-01-01

A general efficient regioselective cobalt catalyzed carbonylation of unactivated C(sp3)–H bonds of aliphatic amides was demonstrated using atmospheric (1–2 atm) carbon monoxide as a C1 source. This straightforward approach provides access to α-spiral succinimide regioselectively in a good yield. Cobalt catalyzed sp3 C–H bond carbonylation is reported for the first time including the functionalization of (β)-C–H bonds of α-1°, 2°, 3° carbons and even internal (β)-C–H bonds. Our initial mechanistic investigation reveals that the C–H activation step is irreversible and will possibly be the rate determining step. PMID:28451350

Current Developments and Challenges in the Search for a Naturally Selected Diels-Alderase

PubMed Central

Kim, Hak Joong; Ruszczycky, Mark W.; Liu, Hung-wen

2012-01-01

Only a very few examples of enzymes known to catalyze pericyclic reactions have been reported, and presently no enzyme has been demonstrated unequivocally to catalyze a Diels-Alder reaction. Nevertheless, research into secondary metabolism has led to the discovery of numerous natural products exhibiting the structural hallmarks of [4+2] cycloadditions, prompting efforts to characterize the responsible enzymatic processes. These efforts have resulted in a growing collection of enzymes believed to catalyze pericyclic [4+2] cycloaddition reactions; however, in each case the complexity of the substrates and catalytic properties of these enzymes poses significant challenges in substantiating these hypotheses. Herein we consider the principles motivating these efforts and the enzymological systems currently under investigation. PMID:22260931

Asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones by rhodium-catalyzed 1,4-addition of arylzinc reagents in the presence of chlorotrimethylsilane.

PubMed

Shintani, Ryo; Yamagami, Takafumi; Kimura, Takahiro; Hayashi, Tamio

2005-11-10

[reaction: see text] The first catalytic asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones has been developed by way of a rhodium-catalyzed 1,4-addition of arylzinc reagents to 4-quinolones. These 1,4-adducts can be obtained with high enantioselectivity by the use of (R)-binap as a ligand, and high yields are realized by conducting the reactions in the presence of chlorotrimethylsilane.

Enantiomerically pure 3-aryl- and 3-hetaryl-2-hydroxypropanoic acids by chemoenzymatic reduction of 2-oxo acids.

PubMed

Sivanathan, Sivatharushan; Körber, Florian; Tent, Jannis Aron; Werner, Svenja; Scherkenbeck, Jürgen

2015-03-06

Phenyllactic acids are found in numerous natural products as well as in active substances used in medicine or plant protection. Enantiomerically pure phenyllactic acids are available by transition-metal-catalyzed hydrogenations or chemoenzymatic reductions of the corresponding 3-aryl-2-oxopropanoic acids. We show here that d-lactate dehydrogenase from Staphylococcus epidermidis reduces a broad spectrum of 2-oxo acids, which are difficult substrates for transition-metal-catalyzed reactions, with excellent enantioselectivities in a simple experimental setup.

First application of an efficient and versatile ligand for copper-catalyzed cross-coupling reactions of vinyl halides with N-heterocycles and phenols.

PubMed

Kabir, M Shahjahan; Lorenz, Michael; Namjoshi, Ojas A; Cook, James M

2010-02-05

2-Pyridin-2-yl-1H-benzoimidazole L3 is presented as a new, efficient, and versatile bidentate N-donor ligand suitable for the copper-catalyzed formation of vinyl C-N and C-O bonds. This inexpensive and easily prepared ligand facilitates copper-catalyzed cross-coupling reactions of alkenyl bromides and iodides with N-heterocycles and phenols to afford the desired cross-coupled products in good to excellent yields with full retention of stereochemistry. This method is particularly noteworthy given its efficiency, that is, mild reaction conditions, low catalyst loading, simplicity, versatility, and exceptional level of functional group tolerance.

First Application of An Efficient and Versatile Ligand for Copper-Catalyzed Cross-Coupling Reactions of Vinyl Halides with N-Heterocycles and Phenols

PubMed Central

Kabir, M. Shahjahan; Lorenz, Michael; Namjoshi, Ojas A.; Cook, James M.

2010-01-01

2-Pyridin-2-yl-1H-benzoimidazole L3 is presented as a new, efficient, and versatile bidentate N-donor ligand suitable for the copper-catalyzed formation of vinyl C-N and C-O bonds. This inexpensive and easily prepared ligand facilitates copper-catalyzed cross-coupling reactions of alkenyl bromides and iodides with N-heterocycles and phenols to afford the desired cross-coupled products in good to excellent yields with full retention of stereochemistry. This method is particularly noteworthy given its efficiency i.e., mild reaction conditions, low catalyst loading, simplicity, versatility, and exceptional level of functional group tolerance. PMID:20039699

Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

USGS Publications Warehouse

Chen, S.G.; Yang, R.T.

1997-01-01

From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

Isomerization of 7-oxabenzonorbornadienes into naphthols catalyzed by [RuCl(2)(CO)(3)](2).

PubMed

Ballantine, Melissa; Menard, Michelle L; Tam, William

2009-10-02

Ruthenium-catalyzed isomerization of 7-oxanorbornadienes into naphthols was investigated. Among the various ruthenium catalysts tested, [RuCl(2)(CO)(3)](2) gave the highest yields in the isomerization, and various substituted naphthols were synthesized in moderate to excellent yields. Both symmetrical and unsymmetrical 7-oxanorbornadienes were employed in the study, and moderate to excellent regioselectivities were observed.

Transesterification of oil mixtures catalyzed by microencapsulated cutinase in reversed micelles.

PubMed

Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S

2010-03-01

Recombinant cutinase from Fusarium solani pisi was used to catalyze the transesterification reaction between a mixture of triglycerides (oils) and methanol in reversed micelles of bis(2-ethylhexyl) sodium sulfosuccinate (AOT) in isooctane for the purposes of producing biodiesel. The use of a bi-phase lipase-catalyzed system brings advantages in terms of catalyst re-use and the control of water activity in the medium and around the enzyme micro-environment. Small-scale batch studies were performed to study the influence of the initial enzyme and alcohol concentrations, and the substrates molar ratio. Conversions in excess of 75 were obtained with reaction times under 24 h, which makes this enzymatic process highly competitive when compared to similar lipase catalyzed reactions for biodiesel production using methanol.

Bimetallic Cobalt-Rhodium Nanoparticle-Catalyzed Reductive Amination of Aldehydes with Nitroarenes Under Atmospheric Hydrogen.

PubMed

Choi, Isaac; Chun, Supill; Chung, Young Keun

2017-12-01

A cobalt-rhodium heterobimetallic nanoparticle (Co 2 Rh 2 /C)-catalyzed tandem reductive amination of aldehydes with nitroaromatics to sec-amines has been developed. The tandem reaction proceeds without any additives under mild conditions (1 atm H 2 and 25 °C). This procedure can be scaled up to the gram scale, and the catalyst can be reused more than six times without loss of activity.

Tailored Cyclic and Linear Polycarbosilazanes by Barium-Catalyzed N-H/H-Si Dehydrocoupling Reactions.

PubMed

Bellini, Clément; Orione, Clément; Carpentier, Jean-François; Sarazin, Yann

2016-03-07

Ba[CH(SiMe3 )2 ]2 (THF)3 catalyzes the fast and controlled dehydrogenative polymerization of Ph2 SiH2 and p-xylylenediamine to afford polycarbosilazanes. The structure (cyclic versus linear; end-groups) and molecular weight of the macromolecules can be tuned by adjusting the Ph2 SiH2 /diamine feed ratio. A detailed analysis of the resulting materials (mol. wt up to ca. 10 000 g mol(-1) ) is provided. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Conversion of cellulose rich municipal solid waste blends using ionic liquids: feedstock convertibility and process scale-up

DOE PAGES

Liang, Ling; Li, Chenlin; Xu, Feng; ...

2017-07-24

For this study, sixteen cellulose rich municipal solid waste (MSW) blends were developed and screened using an acid-assisted ionic liquid (IL) deconstruction process. Corn stover and switchgrass were chosen to represent herbaceous feedstocks; non-recyclable paper (NRP) and grass clippings (GC) collected from households were chosen as MSW candidates given their abundance in municipal waste streams. The most promising MSW blend: corn stover/non-recyclable paper (CS/NRP) at 80/20 ratio was identified in milliliter-scale screening based on the sugar yield, feedstock cost, and availability. A successful scale-up (600-fold) of the IL-acidolysis process on the identified CS/NRP blend has been achieved. The sugar andmore » lignin streams were recovered and characterized. Mass and material energy flows of the optimized process were presented. Feedstock cost for MSW blends was also discussed. Results suggest the promising potential of using MSW as a feedstock blending agent for biorefineries while maintaining sufficient performance and low feedstock cost. The bench scale (6 L) study is an essential step in demonstrating the scalability of this IL technology.« less

Conversion of cellulose rich municipal solid waste blends using ionic liquids: feedstock convertibility and process scale-up

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Ling; Li, Chenlin; Xu, Feng

For this study, sixteen cellulose rich municipal solid waste (MSW) blends were developed and screened using an acid-assisted ionic liquid (IL) deconstruction process. Corn stover and switchgrass were chosen to represent herbaceous feedstocks; non-recyclable paper (NRP) and grass clippings (GC) collected from households were chosen as MSW candidates given their abundance in municipal waste streams. The most promising MSW blend: corn stover/non-recyclable paper (CS/NRP) at 80/20 ratio was identified in milliliter-scale screening based on the sugar yield, feedstock cost, and availability. A successful scale-up (600-fold) of the IL-acidolysis process on the identified CS/NRP blend has been achieved. The sugar andmore » lignin streams were recovered and characterized. Mass and material energy flows of the optimized process were presented. Feedstock cost for MSW blends was also discussed. Results suggest the promising potential of using MSW as a feedstock blending agent for biorefineries while maintaining sufficient performance and low feedstock cost. The bench scale (6 L) study is an essential step in demonstrating the scalability of this IL technology.« less

Synthesis of 5-iodo-1,2,3-triazole-containing macrocycles using copper flow reactor technology.

PubMed

Bogdan, Andrew R; James, Keith

2011-08-05

A new macrocyclization strategy to synthesize 12- to 31-membered 5-iodo-1,2,3-triazole-containing macrocycles is described. The macrocycles have been generated using a simple and efficient copper-catalyzed cycloaddition in flow under environmentally friendly conditions. This methodology also permits the facile, regioselective synthesis of 1,4,5-trisubstituted-1,2,3-triazole-containing macrocyles using palladium-catalyzed cross-coupling reactions. © 2011 American Chemical Society

Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes

PubMed Central

Davis-Gilbert, Zachary W.; Yao, Letitia J.; Tonks, Ian A.

2017-01-01

The inter- or intramolecular oxidative carboamination of alkynes catalyzed by [py2TiCl2NPh]2 is reported. These multicomponent reactions couple alkenes, alkynes and diazenes to form either α,β-unsaturated imines or α-(iminomethyl)cyclopropanes via a TiII/TiIV redox cycle. Each of these products is formed from a common azatitanacyclohexene intermediate that undergoes either β-H elimination or α,γ-coupling, wherein the selectivity is under substrate control. PMID:27790910

Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes.

PubMed

Liwosz, Timothy W; Chemler, Sherry R

2013-06-21

We report herein that potassium alkyltrifluoroborates can be utilized in oxidative Heck-type reactions with vinyl arenes. The reaction is catalyzed by a Cu(OTf)2/1,10-phenanthroline with MnO2 as the stoichiometric oxidant. In addition to the alkyl Heck, amination, esterification, and dimerization reactions of alkyltrifluoroborates are demonstrated under analogous reaction conditions. Evidence for an alkyl radical intermediate is presented.

Preparation of an amphiphilic resin-supported BINAP ligand and its use for rhodium-catalyzed asymmetric 1,4-addition of phenylboronic acid in water.

PubMed

Otomaru, Yusuke; Senda, Taichi; Hayashi, Tamio

2004-09-16

[reaction: see text] The axially chiral bisphosphine ligand, 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (binap), was supported on a polystyrene-poly(ethylene glycol) copolymer (PS-PEG) resin and was used successfully for the rhodium-catalyzed asymmetric 1,4-addition of phenylboronic acid to alpha,beta-unsaturated ketones in water.

Biotransformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine Catalyzed by a NAD(P)H: Nitrate Oxidoreductase from Aspergillus niger

DTIC Science & Technology

2002-01-01

Biotransformation of Hexahydro-1,3,5-trinitro-1,3,5-triazine Catalyzed by a NAD(P)H: Nitrate Oxidoreductase from Aspergillus niger B H A R A T B H U...reductase from Aspergillus niger catalyzed the biotransformation of RDX most effectively at pH 7.0 and 30 °C under anaerobic conditions using NADPH as...nitroreductase. We selected a nitrate reductase (EC 1.6.6.2) from a fungus Aspergillus niger to transform RDX under anaerobic condi- tions because nitrate

Base catalyzed synthesis of bicyclo[3.2.1]octane scaffolds.

PubMed

Boehringer, Régis; Geoffroy, Philippe; Miesch, Michel

2015-07-07

The base-catalyzed reaction of achiral 1,3-cyclopentanediones tethered to activated olefins afforded in high yields bicyclo[3.2.1]octane-6,8-dione or bicyclo[3.2.1]octane-6-carboxylate derivatives bearing respectively three or five stereogenic centers. The course of the reaction is closely related to the reaction time and to the base involved in the reaction.

Nickel-catalyzed asymmetric α-arylation and heteroarylation of ketones with chloroarenes: effect of halide on selectivity, oxidation state, and room-temperature reactions.

PubMed

Ge, Shaozhong; Hartwig, John F

2011-10-19

We report the α-arylation of ketones with a range of aryl chlorides with enantioselectivities from 90 to 99% ee catalyzed by the combination of Ni(COD)(2) and (R)-BINAP and the coupling of ketones with a range of heteroaryl chlorides with enantioselectivities up to 99% ee catalyzed by Ni(COD)(2) and (R)-DIFLUORPHOS. The analogous reactions of bromoarenes occur with much lower enantioselectivities. Mechanistic studies showed that the difference in the rates of decomposition of the arylnickel(II) halide intermediates to {[(R)-BINAP]NiX}(2) likely accounts for the difference in the enantioselectivities of the reactions of bromoarenes and chloroarenes. This catalyst decomposition can be overcome by conducting the reactions with [(R)-BINAP]Ni(η(2)-NC-Ph) (4), which undergoes oxidative addition to haloarenes at room temperature.

Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.01,5]dodecenone

PubMed Central

Inagaki, Fuyuhiko; Itoh, Naoya; Hayashi, Yujiro; Matsui, Yumi

2011-01-01

Summary The [RhCl(CO)dppp]2-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bicyclo[4.3.0]nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson–Khand reaction of the corresponding enynes. This method also provided a new procedure for the construction of the tricyclo[6.4.0.01,5]dodecenone framework in a satisfactory yield. PMID:21512593

Activation and inhibition of CTP synthase from Trypanosoma brucei, the causative agent of African sleeping sickness.

PubMed

Steeves, Craig H; Bearne, Stephen L

2011-09-15

CTP Synthase from Trypanosoma brucei (TbCTPS) catalyzes the conversion of UTP to CTP and is a recognized target for the development of antiprotozoal agents. GTP activates glutamine-dependent CTP formation catalyzed by TbCTPS at concentrations below 0.2 mM, but inhibits this activity at concentrations above 0.2 mM. TbCTPS catalyzes ammonia-dependent CTP formation, which is inhibited by purine derivatives such as GTP, guanosine, caffeine, and uric acid with IC(50) values of 460, 380, 480, and 100 μM, respectively. These observations suggest that the purine ring may serve as a useful scaffold for the development of inhibitors of trypanosomal CTP synthase. Copyright © 2011 Elsevier Ltd. All rights reserved.

Pyrophosphate as substrate for alkaline phosphatase activity: A convenient flow-injection chemiluminescence assay.

PubMed

Zhang, Qingfeng; Zhang, Cuiyun; Yang, Meiding; Yu, Donghong; Yu, Cong

2017-11-01

A sensitive and convenient flow-injection chemiluminescence (FI-CL) turn-on assay for alkaline phosphatase (ALP) activity without any label and synthesis is developed. Cu 2+ can catalyze the luminol-H 2 O 2 CL reaction. Pyrophosphate (PPi) can chelate Cu 2+ and therefore the Cu 2+ -mediated luminol-H 2 O 2 CL reaction is inhibited. The addition of ALP can catalyze the hydrolysis of PPi into phosphate ions, Cu 2+ is released and the chemiluminescence recovers. A detection limit of 1 mU/mL ALP is obtained. Copyright © 2017 John Wiley & Sons, Ltd.

Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

PubMed Central

Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing

2012-01-01

A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

Tandem Cu-catalyzed ketenimine formation and intramolecular nucleophile capture: Synthesis of 1,2-dihydro-2-iminoquinolines from 1-(o-acetamidophenyl)propargyl alcohols

PubMed Central

Kant, Ruchir

2014-01-01

Summary The copper-catalyzed ketenimine formation reaction of 1-(o-acetamidophenyl)propargyl alcohols with various sulfonyl azides is found to undergo a concomitant intramolecular nucleophile attack to generate 1,2-dihydro-2-iminoquinolines after aromatization (via elimination of acetyl and hydroxy groups) and tautomerization. The reaction produces 4-substituted and 3,4-unsubstituted title compounds in moderate to good yields under mild reaction conditions. PMID:24991276

Synthesis of isoflavones by room-temperature nickel-catalyzed cross-couplings of 3-iodo(bromo)chromones with arylzincs.

PubMed

Zhang, Zunting; Qiao, Jinfeng; Wang, Ding; Han, Ling; Ding, Ru

2014-05-01

A new concise, facile method for synthesis of isoflavones was accomplished in moderate to good yields for 3-iodochromones or 3-bromochromones and arylzinc bromides via Negishi cross-coupling reaction catalyzed by NiCl(2)/PPh(3) or NiCl(2)(PPh(3))(2) at room temperature. The Isoflavone core was synthesized in four steps in good yield, starting from commercially available 2-hydroxyacetophenone and aromatic bromide. Three steps of the procedure were carried out at room temperature.

Cationic gold(I) axially chiral biaryl bisphosphine complex-catalyzed atropselective synthesis of heterobiaryls

PubMed Central

Shibuya, Tetsuro; Nakamura, Kyosuke

2011-01-01

Summary It has been established that a cationic gold(I)/(R)-DTBM-Segphos or (R)-BINAP complex catalyzes the atropselective intramolecular hydroarylation of alkynes leading to enantioenriched axially chiral 4-aryl-2-quinolinones and 4-arylcoumarins with up to 61% ee. PMID:21915192

The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

USDA-ARS?s Scientific Manuscript database

The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

Existence of efficient divalent metal ion-catalyzed and inefficient divalent metal ion-independent channels in reactions catalyzed by a hammerhead ribozyme

PubMed Central

Zhou, Jing-Min; Zhou, De-Min; Takagi, Yasuomi; Kasai, Yasuhiro; Inoue, Atsushi; Baba, Tadashi; Taira, Kazunari

2002-01-01

The hammerhead ribozyme is generally accepted as a well characterized metalloenzyme. However, the precise nature of the interactions of the RNA with metal ions remains to be fully defined. Examination of metal ion-catalyzed hammerhead reactions at limited concentrations of metal ions is useful for evaluation of the role of metal ions, as demonstrated in this study. At concentrations of Mn2+ ions from 0.3 to 3 mM, addition of the ribozyme to the reaction mixture under single-turnover conditions enhances the reaction with the product reaching a fixed maximum level. Further addition of the ribozyme inhibits the reaction, demonstrating that a certain number of divalent metal ions is required for proper folding and also for catalysis. At extremely high concentrations, monovalent ions, such as Na+ ions, can also serve as cofactors in hammerhead ribozyme-catalyzed reactions. However, the catalytic efficiency of monovalent ions is extremely low and, thus, high concentrations are required. Furthermore, addition of monovalent ions to divalent metal ion-catalyzed hammerhead reactions inhibits the divalent metal ion-catalyzed reactions, suggesting that the more desirable divalent metal ion–ribozyme complexes are converted to less desirable monovalent metal ion–ribozyme complexes via removal of divalent metal ions, which serve as a structural support in the ribozyme complex. Even though two channels appear to exist, namely an efficient divalent metal ion-catalyzed channel and an inefficient monovalent metal ion-catalyzed channel, it is clear that, under physiological conditions, hammerhead ribozymes are metalloenzymes that act via the significantly more efficient divalent metal ion-dependent channel. Moreover, the observed kinetic data are consistent with Lilley’s and DeRose’s two-phase folding model that was based on ground state structure analyses. PMID:12034824

Identification of the enzymes catalyzing metabolism of methoxyflurane.

PubMed

Waskell, L; Canova-Davis, E; Philpot, R; Parandoush, Z; Chiang, J Y

1986-01-01

The hepatic microsomal metabolism of methoxyflurane in rabbits is markedly stimulated by treatment with phenobarbital. However, the increased rate of metabolism cannot be completely accounted for by the activity of the purified phenobarbital-inducible cytochrome P-450 isozyme 2, even in the presence of cytochrome b5. The discovery of a second hepatic phenobarbital-inducible cytochrome P-450, isozyme 5, led us to undertake experiments to determine in hepatic and pulmonary preparations the portion of microsomal metabolism of methoxyflurane catalyzed by cytochrome P-450 isozymes 2 and 5. We report herein that isozyme 2 accounts for 25% and 29%, respectively, of the O-demethylation of methoxyflurane in hepatic microsomes from untreated and phenobarbital-treated rabbits, and for 25% of the methoxyflurane metabolism in pulmonary microsomes. Results for isozyme 5 indicate that it catalyzes 19% and 27% of methoxyflurane metabolism in control and phenobarbital-induced liver, and 47% of O-demethylation in the lung. In summary, we demonstrate that methoxyflurane O-demethylation in lung, phenobarbital-induced liver, and control liver microsomes is catalyzed by cytochrome P-450 isozymes 2 and 5. Results with purified cytochrome P-450 isozyme 5 are consistent with those obtained using microsomal preparations. Furthermore, metabolism of methoxyflurane by purified isozyme 5 is markedly stimulated by cytochrome b5. A role for cytochrome b5 in cytochrome P-450 isozyme 5-catalyzed metabolism of methoxyflurane was also demonstrated in microsomes. Antibody to isozyme 5 was unable to inhibit methoxyflurane metabolism in the presence of maximally inhibiting concentrations of cytochrome b5 antibody.(ABSTRACT TRUNCATED AT 250 WORDS)

Characterization and optimization of carboxylesterase-catalyzed esterification between capric acid and glycerol for the production of 1-monocaprin in reversed micellar system.

PubMed

Park, Kyung Min; Kwon, Oh Taek; Ahn, Seon Min; Lee, JaeHwan; Chang, Pahn-Shick

2010-02-28

Calotropis procera R. Br. carboxylesterase (EC 3.1.1.1) solubilized in reversed micellar glycerol droplets containing a very small amount of water (less than 5ppm) and stabilized by a surfactant effectively catalyzed the esterification between glycerol and capric acid to produce 1-monocaprin. Reaction variables including surfactant types, organic solvent media, reaction time, G-value ([glycerol]/[capric acid]), R-value ([water]/[surfactant]), pH, temperature, and types of metal ion inhibitors on the carboxylesterase-catalyzed esterification were characterized and optimized to efficiently produce 1-monocaprin. Bis(2-ethylhexyl) sodium sulfosuccinate (AOT) and isooctane were the most effective surfactant and organic solvent medium, respectively, for 1-monocaprin formation in reversed micelles. The optimum G- and R-values were 3.0 and 0.05, respectively, and the optimum pH and temperature were determined to be 10.0 and 60 degrees C, respectively. K(m,app.) and V(max,app.) were calculated from a Hanes-Woolf plot, and the values were 9.64 mM and 2.45 microM/min mg protein, respectively. Among various metal ions, Cu(2+) and Fe(2+) severely inhibited carboxylesterase-catalyzed esterification activity (less than 6.0% of relative activity). Copyright 2009 Elsevier B.V. All rights reserved.

DNA-Catalyzed DNA Cleavage by a Radical Pathway with Well-Defined Products.

PubMed

Lee, Yujeong; Klauser, Paul C; Brandsen, Benjamin M; Zhou, Cong; Li, Xinyi; Silverman, Scott K

2017-01-11

We describe an unprecedented DNA-catalyzed DNA cleavage process in which a radical-based reaction pathway cleanly results in excision of most atoms of a specific guanosine nucleoside. Two new deoxyribozymes (DNA enzymes) were identified by in vitro selection from N 40 or N 100 random pools initially seeking amide bond hydrolysis, although they both cleave simple single-stranded DNA oligonucleotides. Each deoxyribozyme generates both superoxide (O 2 -• or HOO • ) and hydrogen peroxide (H 2 O 2 ) and leads to the same set of products (3'-phosphoglycolate, 5'-phosphate, and base propenal) as formed by the natural product bleomycin, with product assignments by mass spectrometry and colorimetric assay. We infer the same mechanistic pathway, involving formation of the C4' radical of the guanosine nucleoside that is subsequently excised. Consistent with a radical pathway, glutathione fully suppresses catalysis. Conversely, adding either superoxide or H 2 O 2 from the outset strongly enhances catalysis. The mechanism of generation and involvement of superoxide and H 2 O 2 by the deoxyribozymes is not yet defined. The deoxyribozymes do not require redox-active metal ions and function with a combination of Zn 2+ and Mg 2+ , although including Mn 2+ increases the activity, and Mn 2+ alone also supports catalysis. In contrast to all of these observations, unrelated DNA-catalyzed radical DNA cleavage reactions require redox-active metals and lead to mixtures of products. This study reports an intriguing example of a well-defined, DNA-catalyzed, radical reaction process that cleaves single-stranded DNA and requires only redox-inactive metal ions.

Rhodium-Catalyzed Acyloxy Migration of Propargylic Esters in Cycloadditions, Inspiration from Recent “Gold Rush”

PubMed Central

Shu, Xing-Zhong; Shu, Dongxu; Schienebeck, Casi M.

2012-01-01

Transition metal-catalyzed acyloxy migration of propargylic esters offers versatile entries to allene and vinyl carbene intermediates for various fascinating subsequent transformations. Most π-acidic metals (e.g. gold and platinum) are capable of facilitating these acyloxy migration events. However, very few of these processes involve redox chemistry, which are well-known for most other transition metals such as rhodium. The coupling of acyloxy migration of propargylic esters with oxidative addition, migratory insertion, and reductive elimination may lead to ample new opportunities for the design of new reactions. This tutorial review summarizes recent developments in Rh-catalyzed 1,3- and 1,2-acyloxy migration of propargylic esters in a number of cycloaddition reactions. Related Au- and Pt-catalyzed cycloadditions involving acyloxy migration are also discussed. PMID:22895533

Ultra-sensitive non-aggregation colorimetric sensor for detection of iron based on the signal amplification effect of Fe3+ catalyzing H2O2 oxidize gold nanorods.

PubMed

Liu, Jia-Ming; Wang, Xin-Xing; Jiao, Li; Cui, Ma-Lin; Lin, Li-Ping; Zhang, Li-Hong; Jiang, Shu-Lian

2013-11-15

Fe(3+) can catalyze H2O2 to oxidize along on the longitudinal axis of gold nanorods (AuNRs), which caused the aspect ratio of AuNRs to decrease, longitudinal plasmon absorption band (LPAB) of AuNRs to blueshift (Δλ) and the color of the solution to change obviously. Thus, a rapid response and highly sensitive non-aggregation colorimetric sensor for the determination of Fe(3+) has been developed based on the signal amplification effect of catalyzing H2O2 to oxidize AuNRs. This simple and selective sensor with a wide linear range of 0.20-30.00 μM has been utilized to detect Fe(3+) in blood samples, and the results consisted with those obtained by inductively coupled plasma-mass spectroscopy (ICP-MS). Simultaneously, the mechanism of colorimetric sensor for the detection of Fe(3+) was also discussed. Copyright © 2013 Elsevier B.V. All rights reserved.

Excess Substrate is a Spectator Ligand in a Rhodium-Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates with Tolanes

PubMed Central

Oinen, Mark Emil; Yu, Robert T.; Rovis, Tomislav

2009-01-01

Excess substrate has been identified as an unintended spectator ligand affecting enantioselectivity in the [2+2+2] cycloaddition of alkenyl isocyanates with tolanes. Replacement of excess substrate with an exogenous additive affords products with consistent and higher ee’s. The increase in enantioselectivity is the result of a change in composition of a proposed rhodium(III) intermediate on the catalytic cycle. The net result is a rational probe of a short-lived rhodium(III) intermediate, and gives insight that may have applications in many rhodium catalyzed reactions. PMID:19803471

Influence of Pb 2+ ions in the H 2 oxidation on Pt catalyzed hydrogen diffusion anodes in sulfuric acid: presence of oscillatory phenomena

NASA Astrophysics Data System (ADS)

Expósito, E.; Sánchez-Sánchez, C. M.; Solla-Gullón, J.; Montiel, V.

The influence of Pb 2+ ions in sulfuric acid medium on the behavior of a platinum catalyzed hydrogen diffusion electrode (HDE) in a filter press reactor has been studied. A voltammetric study of the H 2 oxidation reaction on a polyoriented platinum electrode and a platinum rotating disk electrode (RDE) in presence of lead ions in solution has also been carried out. Potential oscillations were found in galvanostatic experiments of H 2 oxidation using a HDE catalyzed with platinum when Pb 2+ ions are present in solution. This oscillatory phenomenon was also observed when hydrogen oxidation was carried out in presence of Pb 2+ ions using a platinum RDE. The oscillatory behavior observed has been attributed to an adsorption-oxidation-desorption process of lead on the platinum surface. Due to the low solubility of Pb 2+ in sulfuric acid, at high values of coverage, lead is oxidised to insoluble lead sulfate that blocks the Pt surface. The coupling of the dissolution of lead sulfate and the Pb electrochemical adsorption-oxidation processes cause the oscillatory phenomenon.

Synthesis of "trans"-4,5-Bis-dibenzylaminocyclopent-2-Enone from Furfural Catalyzed by ErCl[subscript 3]·6H[subscript 2]O

ERIC Educational Resources Information Center

Estevão, Mónica S.; Martins, Ricardo J. V.; Alfonso, Carlos A. M.

2017-01-01

An experiment exploring the chemistry of the carbonyl group for the one-step synthesis of "trans"-4,5- dibenzylaminocyclopent-2-enone is described. The reaction of furfural and dibenzylamine in the environmentally friendly solvent ethanol and catalyzed by the Lewis acid ErCl[subscript 3]·6H[subscript 2]O afforded the product in high…

On the Brønsted acid-catalyzed homogeneous hydrolysis of furans.

PubMed

Nikbin, Nima; Caratzoulas, Stavros; Vlachos, Dionisios G

2013-11-01

Furan affairs: Electronic structure calculations of the homogeneous Brønsted acid-catalyzed hydrolysis of 2,5-dimethylfuran show that proton transfer to the β-position is rate-limiting and provides support that the hydrolysis follows general acid catalysis. By means of projected Fukui indices, we show this to be the case for unsubstituted, 2-, and 2,5-substituted furans with electron-donating groups. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-Catalyzed Coupling of 2-Siloxy-1-alkenes and Diazocarbonyl Compounds: Approach to Multisubstituted Furans, Pyrroles, and Thiophenes.

PubMed

Tan, Wei Wen; Yoshikai, Naohiko

2016-07-01

We report herein copper(II)-catalyzed cyclization reactions of silyl enol ethers derived from methyl ketones with α-diazo-β-ketoesters or α-diazoketones to afford 2-siloxy-2,3-dihydrofuran derivatives or 2,3,5-trisubstituted furans, respectively, under mild conditions. The former cyclization products serve as versatile 1,4-diketone surrogates, allowing facile preparation of 2,3,5-trisubstituted furans, pyrroles, and thiophenes.

Rhodium-catalyzed synthesis of silafluorene derivatives via cleavage of silicon-hydrogen and carbon-hydrogen bonds.

PubMed

Ureshino, Tomonari; Yoshida, Takuya; Kuninobu, Yoichiro; Takai, Kazuhiko

2010-10-20

The rhodium-catalyzed synthesis of silafluorenes from biphenylhydrosilanes is described. This highly efficient reaction proceeds via both Si-H and C-H bond activation, producing only H(2) as a side product. Using this method, a ladder-type bis-silicon-bridged p-terphenyl could also be synthesized.

53. VIEW LOOKING S.E. AT THE CATALYZER BUILDINGS, COOLING SHEDS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

53. VIEW LOOKING S.E. AT THE CATALYZER BUILDINGS, COOLING SHEDS AND ABSORPTION BUILDINGS IN THE BACKGROUND. MAY 29, 1919. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

Enantioselective Synthesis of Chiral Cyclopent-2-enones by Nickel-Catalyzed Desymmetrization of Malonate Esters.

PubMed

Karad, Somnath Narayan; Panchal, Heena; Clarke, Christopher; Lewis, William; Lam, Hon Wai

2018-05-16

The enantioselective synthesis of highly functionalized chiral cyclopent-2-enones by the reaction of alkynyl malonate esters with arylboronic acids is described. These desymmetrizing arylative cyclizations are catalyzed by a chiral phosphinooxazoline-nickel complex, and cyclization is enabled by the reversible E/Z isomerization of alkenylnickel species. The general methodology is also applicable to the synthesis of 1,6-dihydropyridin-3(2H)-ones. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

BF3·Et2O Catalysed 4-Aryl-3-phenyl-benzopyrones, Pro-SERMs, and Their Characterization

PubMed Central

Srivastava, Ambika; Kumar, Rajesh

2015-01-01

We have synthesized the novel 4-(4-hydroxy-benzyl)-3-phenyl-chromen-2-one which is a precursor of SERMs with a smaller number of steps and good yield. Two methodologies for the synthesis have been worked out. Anhydrous BF3·Et2O catalyzed reaction was found to be selective for product formation while anhydrous AlCl3, FeCl3, and SnCl4 catalyzed ones were nonselective. PMID:26421007

Nickel-catalyzed sp2 C-H bonds arylation of N-aromatic heterocycles with Grignard reagents at room temperature.

PubMed

Qu, Gui-Rong; Xin, Peng-Yang; Niu, Hong-Ying; Wang, Dong-Chao; Ding, Rui-Fang; Guo, Hai-Ming

2011-10-21

A novel protocol for nickel-catalyzed direct sp(2) C-H bond arylation of purines has been developed. This new reaction proceeded efficiently at room temperature using Grignard reagent as the coupling partner within 5 hours in good to high yields. This approach provides a new access to a variety of C8-arylpurines which are potentially of great importance in medicinal chemistry.

Large enhancement of oscillating chemiluminescence with [Ru(bpy)3 ](2+) -catalyzed Belousov-Zhabotinsky reaction in the presence of tri-n-propylamine.

PubMed

Lan, Xiaolan; Zheng, Baozhan; Zhao, Yan; Yuan, Hongyan; Du, Juan; Xiao, Dan

2013-01-01

Oscillating chemiluminescence enhanced by the addition of tri-n-propylamine (TPrA) to the typical Belousov-Zhabotinsky (BZ) reaction system catalyzed by ruthenium(II)tris(2.2'-bipyridine)(Ru(bpy)3 (2+) ) was investigated using a luminometry method. The [Ru(bpy)3 ](2+) /TPrA system was first used as the catalyst for a BZ oscillator in a closed system, which exhibited a shorter induction period, higher amplitude and much more stable chemiluminescence (CL) oscillation. The effects of various concentrations of TPrA, oxygen and nitrogen flow rate on the oscillating behavior of this system were examined. In addition, the CL intensity of the [Ru(bpy)3 ](2+) /TPrA-BZ system was found to be inhibited by phenol, thus providing a way for use of the BZ system in the determination of phenolic compounds. Moreover, the possible mechanism of the oscillating CL reaction catalyzed by [Ru(bpy)3 ](2+) /TPrA and the inhibition effects of oxygen and phenol on this oscillating CL system were considered. Copyright © 2012 John Wiley & Sons, Ltd.

Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation.

PubMed

Sequeira, Fatima C; Bovino, Michael T; Chipre, Anthony J; Chemler, Sherry R

2012-05-01

(S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure.

Multigram Synthesis of a Chiral Substituted Indoline Via Copper-Catalyzed Alkene Aminooxygenation

PubMed Central

Sequeira, Fatima C.; Bovino, Michael T.; Chipre, Anthony J.

2012-01-01

(S)-5-Fluoro-2-(2,2,6,6-tetramethylpiperidin-1-yloxymethyl)-1-tosylindoline, a 2-methyleneoxy-substituted chiral indoline, was synthesized on multigram scale using an efficient copper-catalyzed enantioselective intramolecular alkene aminooxygenation. The synthesis is accomplished in four steps and the indoline is obtained in 89% ee (>98% after one recrystallization). Other highlights include efficient gram-scale synthesis of the (4R,5S)-di-Ph-box ligand and efficient separation of a monoallylaniline from its bis(allyl)aniline by-product by distillation under reduced pressure. PMID:22639473

Carbon nanotube substrates and catalyzed hot stamp for polishing and patterning the substrates

DOEpatents

Wang, Yuhuang [Evanston, IL; Hauge, Robert H [Houston, TX; Schmidt, Howard K [Houston, TX; Kim, Myung Jong [Houston, TX; Kittrell, W Carter [Houston, TX

2009-09-08

The present invention is generally directed to catalyzed hot stamp methods for polishing and/or patterning carbon nanotube-containing substrates. In some embodiments, the substrate, as a carbon nanotube fiber end, is brought into contact with a hot stamp (typically at 200-800.degree. C.), and is kept in contact with the hot stamp until the morphology/patterns on the hot stamp have been transferred to the substrate. In some embodiments, the hot stamp is made of material comprising one or more transition metals (Fe, Ni, Co, Pt, Ag, Au, etc.), which can catalyze the etching reaction of carbon with H.sub.2, CO.sub.2, H.sub.2O, and/or O.sub.2. Such methods can (1) polish the carbon nanotube-containing substrate with a microscopically smooth finish, and/or (2) transfer pre-defined patterns from the hot stamp to the substrate. Such polished or patterned carbon nanotube substrates can find application as carbon nanotube electrodes, field emitters, and field emitter arrays for displays and electron sources.

Cu-catalyzed formal methylative and hydrogenative carboxylation of alkynes with carbon dioxide: efficient synthesis of α,β-unsaturated carboxylic acids.

PubMed

Takimoto, Masanori; Hou, Zhaomin

2013-08-19

The sequential hydroalumination or methylalumination of various alkynes catalyzed by different catalyst systems, such those based on Sc, Zr, and Ni complexes, and the subsequent carboxylation of the resulting alkenylaluminum species with CO2 catalyzed by an N-heterocyclic carbene (NHC)-copper catalyst have been examined in detail. The regio- and stereoselectivity of the overall reaction relied largely on the hydroalumination or methylalumination reactions, which significantly depended on the catalyst and alkyne substrates. The subsequent Cu-catalyzed carboxylation proceeded with retention of the stereoconfiguration of the alkenylaluminum species. All the reactions could be carried out in one-pot to afford efficiently a variety of α,β-unsaturated carboxylic acids with well-controlled configurations, which are difficult to construct by previously reported methods. This protocol could be practically useful and attractive because of its high regio- and stereoselectivity, simple one-pot reaction operation, and the use of CO2 as a starting material. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic asymmetric enyne addition to aldehdyes and Rh(I)-catalyzed stereoselective domino Pauson-Khand/[4 + 2] cycloaddition.

PubMed

Chen, Wei; Tay, Jia-Hui; Ying, Jun; Yu, Xiao-Qi; Pu, Lin

2013-03-15

The 1,1'-bi-2-naphthol-ZnEt2-Ti(O(i)Pr)4-Cy2NH system is found to catalyze the 1,3-enyne addition to aliphatic aldehydes as well as other aldehydes at room temperature with 75-96% yield and 82-97% ee. This system is also broadly applicable for the highly enantioselective reaction of other alkyl-, aryl-, and silylalkynes with structurally diverse aldehydes. The propargylic alcohols prepared from the catalytic asymmetric enyne addition to aliphatic aldehydes are used to prepare a series of optically active trienynes. In the presence of a catalytic amount of [RhCl(CO)2]2 and 1 atm of CO, the optically active trienynes undergo highly stereoselective domino Pauson-Khand/[4 + 2] cycloaddition to generate optically active multicyclic products. The Rh(I) catalyst is also found to catalyze the coupling of a diyne with CO followed by [4 + 2] cycloaddition to generate an optically active multicyclic product. These transformations are potentially useful for the asymmetric synthesis of polyquinanes containing a quaternary chiral carbon center.

Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block.

PubMed

Mastalir, Matthias; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

2017-07-05

This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, indoles, carbazoles, and thiophenes in combination with amines and MeOH as a C1 source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.

Reactivity of bromoselenophenes in palladium-catalyzed direct arylations.

PubMed

Skhiri, Aymen; Ben Salem, Ridha; Soulé, Jean-François; Doucet, Henri

2017-01-01

The reactivity of 2-bromo- and 2,5-dibromoselenophenes in Pd-catalyzed direct heteroarylation was investigated. From 2-bromoselenophene, only the most reactive heteroarenes could be employed to prepare 2-heteroarylated selenophenes; whereas, 2,5-dibromoselenophene generally gave 2,5-di(heteroarylated) selenophenes in high yields using both thiazole and thiophene derivatives. Moreover, sequential catalytic C2 heteroarylation, bromination, catalytic C5 arylation reactions allowed the synthesis of unsymmetrical 2,5-di(hetero)arylated selenophene derivatives in three steps from selenophene.

Efficient production of free fatty acids from ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate.

PubMed

Mi, Le; Qin, Dandan; Cheng, Jie; Wang, Dan; Li, Sha; Wei, Xuetuan

2017-03-01

Two engineered Escherichia coli strains, DQ101 (MG1655 fadD - )/pDQTES and DQ101 (MG1655 fadD - )/pDQTESZ were constructed to investigate the free fatty acid production using ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate as carbon source in this study. The plasmid, pDQTES, carrying an acyl-ACP thioesterase 'TesA of E. coli in pTrc99A was constructed firstly, and then (3R)-hydroxyacyl-ACP dehydratase was ligated after the TesA to give the plasmid pDQTESZ. These two strains exhibited efficient fatty acid production when glucose was used as the sole carbon source, with a final concentration of 2.45 and 3.32 g/L, respectively. The free fatty acid production of the two strains on xylose is not as efficient as that on glucose, which was 2.32 and 2.96 g/L, respectively. For mixed sugars, DQ101 (MG1655 fadD - )-based strains utilized glucose and pentose sequentially under the carbon catabolite repression (CCR) regulation. The highest total FFAs concentration from the mixed sugar culture reached 2.81 g/L by DQ101 (MG1655 fadD - )/pDQTESZ. Furthermore, when ionic liquid-based enzyme-catalyzed bamboo hydrolysate was used as the carbon source, the strain DQ101 (MG1655 fadD - )/pDQTESZ could produce 1.23 g/L FFAs with a yield of 0.13 g/g, and while it just produced 0.65 g/L free fatty acid with the ionic liquid-based acid-catalyzed bamboo hydrolysate as the feedstock. The results suggested that enzymatic catalyzed bamboo hydrolysate with ionic liquid pretreatment could serve as an efficient feedstock for free fatty acid production.

NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones.

PubMed

Takaki, Ken; Hino, Makoto; Ohno, Akira; Komeyama, Kimihiro; Yoshida, Hiroto; Fukuoka, Hiroshi

2017-01-01

Thiazolium carbene-catalyzed reactions of 1,2-diketones and 1,2,3-triketones with enones and ynones have been investigated. The diketones gave α,β-double acylation products via unique Breslow intermediates isolable as acid salts, whereas the triketones formed stable adducts with the NHC instead of the coupling products.

NHC-catalyzed cleavage of vicinal diketones and triketones followed by insertion of enones and ynones

PubMed Central

Hino, Makoto; Ohno, Akira; Komeyama, Kimihiro; Yoshida, Hiroto; Fukuoka, Hiroshi

2017-01-01

Thiazolium carbene-catalyzed reactions of 1,2-diketones and 1,2,3-triketones with enones and ynones have been investigated. The diketones gave α,β-double acylation products via unique Breslow intermediates isolable as acid salts, whereas the triketones formed stable adducts with the NHC instead of the coupling products. PMID:28904625

Copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines: synthesis of imidazopyridine derivatives.

PubMed

Yu, Jipan; Jin, Yunhe; Zhang, Hao; Yang, Xiaobo; Fu, Hua

2013-12-02

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper-catalyzed aerobic oxidative C-H functionalization of substituted pyridines with N-(alkylidene)-4H-1,2,4-triazol-4-amines. The procedure occurs by cleavage of the N-N bond in the N-(alkylidene)-4H-1,2,4-triazol-4-amines and activation of an aryl C-H bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition-metal-catalyzed C-H functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diversity-oriented asymmetric catalysis (DOAC): stereochemically divergent synthesis of thiochromanes using an imidazoline-aminophenol-nickel-catalyzed Michael/Henry reaction.

PubMed

Arai, Takayoshi; Yamamoto, Yushi

2014-03-21

The (S,S)-diphenylethylenediamine-derived imidazoline-aminophenol-Ni complex catalyzed tandem asymmetric Michael/Henry reaction of 2-mercaptobenzaldehydes with β-nitrostyrenes to give the corresponding (2S,3R,4R)-2-aryl-3-nitrothiochroman-4-ols in up to 99% diastereoselectivity with 95% ee was demonstrated in diversity-oriented asymmetric catalysis. Reduction of the nitro group of the chiral thiochromanes gave a new series of (2S,3R,4R)-3-amino-2-arylthiochroman-4-ols with retention of the strereoselectivity.

Copper-catalyzed oxidative C-O bond formation of 2-acyl phenols and 1,3-dicarbonyl compounds with ethers: direct access to phenol esters and enol esters.

PubMed

Park, Jihye; Han, Sang Hoon; Sharma, Satyasheel; Han, Sangil; Shin, Youngmi; Mishra, Neeraj Kumar; Kwak, Jong Hwan; Lee, Cheong Hoon; Lee, Jeongmi; Kim, In Su

2014-05-16

A copper-catalyzed oxidative coupling of 2-carbonyl-substituted phenols and 1,3-dicarbonyl compounds with a wide range of dibenzyl or dialkyl ethers is described. This protocol provides an efficient preparation of phenol esters and enol esters in good yields with high chemoselectivity. This method represents an alternative protocol for classical esterification reactions.

Coupled ferredoxin and crotonyl coenzyme A (CoA) reduction with NADH catalyzed by the butyryl-CoA dehydrogenase/Etf complex from Clostridium kluyveri.

PubMed

Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K

2008-02-01

Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0' = -410 mV) with NADH (E0' = -320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0' = -10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper.

Novel Dry-Type Glucose Sensor Based on a Metal-Oxide-Semiconductor Capacitor Structure with Horseradish Peroxidase + Glucose Oxidase Catalyzing Layer

NASA Astrophysics Data System (ADS)

Lin, Jing-Jenn; Wu, You-Lin; Hsu, Po-Yen

2007-10-01

In this paper, we present a novel dry-type glucose sensor based on a metal-oxide-semiconductor capacitor (MOSC) structure using SiO2 as a gate dielectric in conjunction with a horseradish peroxidase (HRP) + glucose oxidase (GOD) catalyzing layer. The tested glucose solution was dropped directly onto the window opened on the SiO2 layer, with a coating of HRP + GOD catalyzing layer on top of the gate dielectric. From the capacitance-voltage (C-V) characteristics of the sensor, we found that the glucose solution can induce an inversion layer on the silicon surface causing a gate leakage current flowing along the SiO2 surface. The gate current changes Δ I before and after the drop of glucose solution exhibits a near-linear relationship with increasing glucose concentration. The Δ I sensitivity is about 1.76 nA cm-2 M-1, and the current is quite stable 20 min after the drop of the glucose solution is tested.

Stereoselective isoxazolidine synthesis via copper-catalyzed alkene aminooxygenation.

PubMed

Karyakarte, Shuklendu D; Smith, Thomas P; Chemler, Sherry R

2012-09-07

Isoxazolidines are useful in organic synthesis, drug discovery, and chemical biology endeavors. A new stereoselective synthesis of methyleneoxy-substituted isoxazolidines is disclosed. The method involves copper-catalyzed aminooxygenation/cyclization of N-sulfonyl-O-butenyl hydroxylamines in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl radical (TEMPO) and O(2) and provides substituted isoxazolidines in excellent yields and diastereoselectivities. We also demonstrate selective mono N-O reduction followed by oxidation of the remaining N-O bond to reveal a 2-amino-γ-lactone. Reduction of the γ-lactone reveals the corresponding aminodiol.

Anisotropic Morphological Changes in Goethite during Fe(2+)-Catalyzed Recrystallization.

PubMed

Joshi, Prachi; Gorski, Christopher A

2016-07-19

When goethite is exposed to aqueous Fe(2+), rapid and extensive Fe atom exchange can occur between solid-phase Fe(3+) and aqueous Fe(2+) in a process referred to as Fe(2+)-catalyzed recrystallization. This process can lead to the structural incorporation or release of trace elements, which has important implications for contaminant remediation and nutrient biogeochemical cycling. Prior work found that the process did not cause major changes to the goethite structure or morphology. Here, we further investigated if and how goethite morphology and aggregation behavior changed temporally during Fe(2+)-catalyzed recrystallization. On the basis of existing literature, we hypothesized that Fe(2+)-catalyzed recrystallization of goethite would not result in changes to individual particle morphology or interparticle interactions. To test this, we reacted nanoparticulate goethite with aqueous Fe(2+) at pH 7.5 over 30 days and used transmission electron microscopy (TEM), cryogenic TEM, and (55)Fe as an isotope tracer to observe changes in particle dimensions, aggregation, and isotopic composition over time. Over the course of 30 days, the goethite particles substantially recrystallized, and the particle dimensions changed anisotropically, resulting in a preferential increase in the mean particle width. The temporal changes in goethite morphology could not be completely explained by a single mineral-transformation mechanism but rather indicated that multiple transformation mechanisms occurred concurrently. Collectively, these results demonstrate that the morphology of goethite nanoparticles does change during recrystallization, which is an important step toward identifying the driving force(s) of recrystallization.

Amide to Alkyne Interconversion via a Nickel/Copper-Catalyzed Deamidative Cross-Coupling of Aryl and Alkenyl Amides.

PubMed

Srimontree, Watchara; Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Rueping, Magnus

2017-06-16

A nickel-catalyzed deamidative cross-coupling reaction of amides with terminal alkynes as coupling partners was disclosed. This newly developed methodology allows the direct interconversion of amides to alkynes and enables a facile route for C(sp2)-C(sp) bond formation in a straightforward and mild fashion.

Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source.

PubMed

Furusawa, Takuma; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Tanimoto, Hiroki; Kakiuchi, Kiyomi

2016-08-19

Synthesis of fluoren-9-ones by a Rh-catalyzed intramolecular C-H/C-I carbonylative coupling of 2-iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate-determining step is not a C-H bond cleavage but, rather, the oxidative addition of the C-I bond to a Rh(I) center. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Clostridium acidurici electron-bifurcating formate dehydrogenase.

PubMed

Wang, Shuning; Huang, Haiyan; Kahnt, Jörg; Thauer, Rudolf K

2013-10-01

Cell extracts of uric acid-grown Clostridium acidurici catalyzed the coupled reduction of NAD(+) and ferredoxin with formate at a specific activity of 1.3 U/mg. The enzyme complex catalyzing the electron-bifurcating reaction was purified 130-fold and found to be composed of four subunits encoded by the gene cluster hylCBA-fdhF2.

Homogeneous dihydroxylation of olefins catalyzed by OsO(4)(2-) immobilized on a dendritic backbone with a tertiary nitrogen at its core position.

PubMed

Fujita, Ken-Ichi; Inoue, Kensuke; Tsuchimoto, Teruhisa; Yasuda, Hiroyuki

2012-01-01

OsO(4)(2-) immobilized on a poly(benzyl ether) dendrimer with a tertiary nitrogen at its core position efficiently catalyzed the homogeneous dihydroxylation of olefins with a low level of osmium leaching. The dendritic osmium catalyst could be applied to the wide range of olefins. Furthermore, the dendritic osmium catalyst was recovered by reprecipitation and then reused up to five times.

Glycerolipid Headgroups Control Rate and Mechanism of Superoxide Dismutase-1 Aggregation and Accelerate Fibrillization of Slowly Aggregating Amyotrophic Lateral Sclerosis Mutants.

PubMed

Rasouli, Sanaz; Abdolvahabi, Alireza; Croom, Corbin M; Plewman, Devon L; Shi, Yunhua; Shaw, Bryan F

2018-04-20

Interactions between superoxide dismutase-1 (SOD1) and lipid membranes might be directly involved in the toxicity and intercellular propagation of aggregated SOD1 in amyotrophic lateral sclerosis (ALS), but the chemical details of lipid-SOD1 interactions and their effects on SOD1 aggregation remain unclear. This paper determined the rate and mechanism of nucleation of fibrillar apo-SOD1 catalyzed by liposomal surfaces with identical hydrophobic chains (RCH 2 (O 2 C 18 H 33 ) 2 ), but headgroups of different net charge and hydrophobicity (i.e., R(CH 2 )N + (CH 3 ) 3 , RPO 4 - (CH 2 ) 2 N + (CH 3 ) 3 , and RPO 4 - ). Under semiquiescent conditions (within a 96 well microplate, without a gyrating bead), the aggregation of apo-SOD1 into thioflavin-T-positive (ThT(+)) amyloid fibrils did not occur over 120 h in the absence of liposomal surfaces. Anionic liposomes triggered aggregation of apo-SOD1 into ThT(+) amyloid fibrils; cationic liposomes catalyzed fibrillization but at slower rates and across a narrower lipid concentration; zwitterionic liposomes produced nonfibrillar (amorphous) aggregates. The inability of zwitterionic liposomes to catalyze fibrillization and the dependence of fibrillization rate on anionic lipid concentration suggests that membranes catalyze SOD1 fibrillization by a primary nucleation mechanism. Membrane-catalyzed fibrillization was also examined for eight ALS variants of apo-SOD1, including G37R, G93R, D90A, and E100G apo-SOD1 that nucleate slower than or equal to WT SOD1 in lipid-free, nonquiescent amyloid assays. All ALS variants (with one exception) nucleated faster than WT SOD1 in the presence of anionic liposomes, wherein the greatest acceleratory effects were observed among variants with lower net negative surface charge (G37R, G93R, D90A, E100G). The exception was H46R apo-SOD1, which did not form ThT(+) species.

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

Palladium-Catalyzed α-Arylation of 2-Chloroacetates and 2-Chloroacetamides

PubMed Central

Traister, Kaitlin M.; Barcellos, Thiago

2013-01-01

A method has been developed for the Pd-catalyzed synthesis of α-(hetero)aryl esters and amides through a Suzuki–Miyaura cross-coupling reaction. This method avoids the use of strong base, does not necessitate inert or low temperature formation of reagents, and does not require the use of a large excess of organometallic reagent. Utilization of organotrifluoroborate salts as nucleophilic partners allows a variety of functional groups and heterocyclic compounds to be tolerated. PMID:23570264

Nickel-catalyzed hydrocarboxylation of ynamides with CO2 and H2O: observation of unexpected regioselectivity.

PubMed

Doi, Ryohei; Abdullah, Iman; Taniguchi, Takahisa; Saito, Nozomi; Sato, Yoshihiro

2017-07-06

We describe the nickel-catalyzed hydrocarboxylation of ynamides with CO 2 and H 2 O to afford a variety of α-amino-α,β-unsaturated esters with high regioselectivities. The selective α-carboxylation of ynamides with this catalytic protocol is unexpected in view of the electronic bias of ynamides and is in sharp contrast to our previous study in which a stoichiometric amount of Ni(0) was used to form a β-carboxylated product exclusively. We revealed that this unexpected C-C bond formation was induced by the combination of Zn and MgBr 2 .

Codominant Expression of N-Acetylation and O-Acetylation Activities Catalyzed by N-Acetyltransferase 2 in Human Hepatocytes

PubMed Central

Doll, Mark A.; Zang, Yu; Moeller, Timothy

2010-01-01

Human populations exhibit genetic polymorphism in N-acetylation capacity, catalyzed by N-acetyltransferase 2 (NAT2). We investigated the relationship between NAT2 acetylator genotype and phenotype in cryopreserved human hepatocytes. NAT2 genotypes determined in 256 human samples were assigned as rapid (two rapid alleles), intermediate (one rapid and one slow allele), or slow (two slow alleles) acetylator phenotypes based on functional characterization of the NAT2 alleles reported previously in recombinant expression systems. A robust and significant relationship was observed between deduced NAT2 phenotype (rapid, intermediate, or slow) and N-acetyltransferase activity toward sulfamethazine (p < 0.0001) and 4-aminobiphenyl (p < 0.0001) and for O-acetyltransferase-catalyzed metabolic activation of N-hydroxy-4-aminobiphenyl (p < 0.0001), N-hydroxy-2-amino-3,8-dimethylimidazo[4,5-f] quinoxaline (p < 0.01), and N-hydroxy-2-amino-1-methyl-6-phenylimidazo[4,5-b] pyridine (p < 0.0001). NAT2-specific protein levels also significantly associated with the rapid, intermediate, and slow NAT2 acetylator phenotypes (p < 0.0001). As a negative control, p-aminobenzoic acid (an N-acetyltransferase 1-selective substrate) N-acetyltransferase activities from the same samples did not correlate with the three NAT2 acetylator phenotypes (p > 0.05). These results clearly document codominant expression of human NAT2 alleles resulting in rapid, intermediate, and slow acetylator phenotypes. The three phenotypes reflect levels of NAT2 protein catalyzing both N- and O-acetylation. Our results suggest a significant role of NAT2 acetylation polymorphism in arylamine-induced cancers and are consistent with differential cancer risk and/or drug efficacy/toxicity in intermediate compared with rapid or slow NAT2 acetylator phenotypes. PMID:20430842

A General, Concise Strategy that Enables Collective Total Syntheses of over 50 Protoberberine and Five Aporhoeadane Alkaloids within Four to Eight Steps.

PubMed

Zhou, Shiqiang; Tong, Rongbiao

2016-05-17

A concise, catalytic, and general strategy that allowed efficient total syntheses of 22 natural 13-methylprotoberberines within four steps for each molecule is reported. This synthesis represents the most efficient and shortest route to date, featuring three catalytic processes: CuI-catalyzed redox-A(3) reaction, Pd-catalyzed reductive carbocyclization, and PtO2 -catalyzed hydrogenation. Importantly, this new strategy to the tetracyclic framework has also been applied to the collective concise syntheses of >30 natural protoberberines (without 13-methyl group) and five aporhoeadane alkaloids. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pd-catalyzed versus uncatalyzed, PhI(OAc)2-mediated cyclization reactions of N6-([1,1'-biaryl]-2-yl)adenine nucleosides.

PubMed

Satishkumar, Sakilam; Poudapally, Suresh; Vuram, Prasanna K; Gurram, Venkateshwarlu; Pottabathini, Narender; Sebastian, Dellamol; Yang, Lijia; Pradhan, Padmanava; Lakshman, Mahesh K

2017-11-09

In this work we have assessed reactions of N 6 -([1,1'-biaryl]-2-yl)adenine nucleosides with Pd(OAc) 2 and PhI(OAc) 2 , via a Pd II /Pd IV redox cycle. The substrates are readily obtained by Pd/Xantphos-catalyzed reaction of adenine nucleosides with 2-bromo-1,1'-biaryls. In PhMe, the N 6 -biarylyl nucleosides gave C6-carbazolyl nucleoside analogues by C-N bond formation with the exocyclic N 6 nitrogen atom. In the solvent screening for the Pd-catalyzed reactions, an uncatalyzed process was found to be operational. It was observed that the carbazolyl products could also be obtained in the absence of a metal catalyst by reaction with PhI(OAc) 2 in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). Thus, under Pd catalysis and in HFIP, reactions proceed to provide carbazolyl nucleoside analogues, with some differences. If reactions of N 6 -biarylyl nucleoside substrates were conducted in MeCN, formation of aryl benzimidazopurinyl nucleoside derivatives was observed in many cases by C-N bond formation with the N 1 ring nitrogen atom of the purine (carbazole and benzimidazole isomers are readily separated by chromatography). Whereas Pd II /Pd IV redox is responsible for carbazole formation under the metal-catalyzed conditions, in HFIP and MeCN radical cations and/or nitrenium ions can be intermediates. An extensive set of radical inhibition experiments was conducted and the data are presented.

A Glutathione S-Transferase Catalyzes the Dehalogenation of Inhibitory Metabolites of Polychlorinated Biphenyls

PubMed Central

Fortin, Pascal D.; Horsman, Geoff P.; Yang, Hao M.; Eltis, Lindsay D.

2006-01-01

BphK is a glutathione S-transferase of unclear physiological function that occurs in some bacterial biphenyl catabolic (bph) pathways. We demonstrated that BphK of Burkholderia xenovorans strain LB400 catalyzes the dehalogenation of 3-chloro 2-hydroxy-6-oxo-6-phenyl-2,4-dienoates (HOPDAs), compounds that are produced by the cometabolism of polychlorinated biphenyls (PCBs) by the bph pathway and that inhibit the pathway's hydrolase. A one-column protocol was developed to purify heterologously produced BphK. The purified enzyme had the greatest specificity for 3-Cl HOPDA (kcat/Km, ∼104 M−1 s−1), which it dechlorinated approximately 3 orders of magnitude more efficiently than 4-chlorobenzoate, a previously proposed substrate of BphK. The enzyme also catalyzed the dechlorination of 5-Cl HOPDA and 3,9,11-triCl HOPDA. By contrast, BphK did not detectably transform HOPDA, 4-Cl HOPDA, or chlorinated 2,3-dihydroxybiphenyls. The BphK-catalyzed dehalogenation proceeded via a ternary-complex mechanism and consumed 2 equivalents of glutathione (GSH) (Km for GSH in the presence of 3-Cl HOPDA, ∼0.1 mM). A reaction mechanism consistent with the enzyme's specificity is proposed. The ability of BphK to dehalogenate inhibitory PCB metabolites supports the hypothesis that this enzyme was recruited to facilitate PCB degradation by the bph pathway. PMID:16740949

Pyridine synthesis by reactions of allyl amines and alkynes proceeding through a Cu(OAc)2 oxidation and Rh(III)-catalyzed N-annulation sequence.

PubMed

Kim, Dong-Su; Park, Jung-Woo; Jun, Chul-Ho

2012-11-28

A new methodology has been developed for the synthesis of pyridines from allyl amines and alkynes, which involves sequential Cu(II)-promoted dehydrogenation of the allylamine and Rh(III)-catalyzed N-annulation of the resulting α,β-unsaturated imine and alkyne.

Convenient synthesis of benzothiazoles and benzimidazoles through Brønsted acid catalyzed cyclization of 2-amino thiophenols/anilines with β-diketones.

PubMed

Mayo, Muhammad Shareef; Yu, Xiaoqiang; Zhou, Xiaoyu; Feng, Xiujuan; Yamamoto, Yoshinori; Bao, Ming

2014-02-07

Brønsted acid catalyzed cyclization reactions of 2-amino thiophenols/anilines with β-diketones under oxidant-, metal-, and radiation-free conditions are described. Various 2-substituted benzothiazoles/benzimidazoles are obtained in satisfactory to excellent yields. Different groups such as methyl, chloro, nitro, and methoxy linked on benzene rings were tolerated under the optimized reaction conditions.

Carbon isotope fractionation of 1,1,1-trichloroethane during base-catalyzed persulfate treatment.

PubMed

Marchesi, Massimo; Thomson, Neil R; Aravena, Ramon; Sra, Kanwartej S; Otero, Neus; Soler, Albert

2013-09-15

The extent of carbon isotope fractionation during degradation of 1,1,1-trichloroethane (1,1,1-TCA) by a base-catalyzed persulfate (S₂O₈(2-)) treatment system was investigated. Significant destruction of 1,1,1-TCA was observed at a pH of ∼12. An increase in the NaOH:S₂O₈(2-) molar ratio from 0.2:1 to 8:1 enhanced the reaction rate of 1,1,1-TCA by a factor of ∼5 to yield complete (>99.9%) destruction. An average carbon isotope enrichment fractionation factor which was independent of the NaOH:S₂O₈(2-) molar ratio of -7.0 ± 0.2‰ was obtained. This significant carbon isotope fractionation and the lack of dependence on changes in the NaOH:S₂O₈(2-) molar ratio demonstrates that carbon isotope analysis can potentially be used in situ as a performance assessment tool to estimate the degradation effectiveness of 1,1,1-TCA by a base-catalyzed persulfate system. Copyright © 2013 Elsevier B.V. All rights reserved.

Imidazole catalyzes chlorination by unreactive primary chloramines

PubMed Central

Roemeling, Margo D.; Williams, Jared; Beckman, Joseph S.; Hurst, James K.

2015-01-01

Hypochlorous acid and simple chloramines (RNHCl) are stable biologically-derived chlorinating agents. In general, the chlorination potential of HOCl is much greater than that of RNHCl, allowing it to oxidize or chlorinate a much wider variety of reaction partners. However, in this study we demonstrate by kinetic analysis that the reactivity of RNHCl can be dramatically promoted by imidazole and histidyl model compounds via intermediary formation of the corresponding imidazole chloramines. Two biologically relevant reactions were investigated—loss of imidazole-catalyzed chlorinating capacity and phenolic ring chlorination using fluorescein and the tyrosine analog, 4-hydroxyphenylacetic acid (HPA). HOCl reacted stoichiometrically with imidazole, N-acetylhistidine (NAH), or imidazoleacetic acid to generate the corresponding imidazole chloramines which subsequently decomposed. Chloramine (NH2Cl) also underwent a markedly accelerated loss in chlorinating capacity when NAH was present, although in this case NAHCl did not accumulate, indicating that the catalytic intermediate must be highly reactive. Mixing HOCl with 1-methylimidazole (MeIm) led to very rapid loss in chlorinating capacity via formation of a highly reactive chlorinium ion (MeImCl+) intermediate; this behavior suggests that the reactive forms of the analogous imidazole chloramines are their conjugate acids, e.g., the imidazolechlorinium ion (HImCl+). HOCl-generated imidazole chloramine (ImCl) reacted rapidly with fluorescein in a specific acid-catalyzed second order reaction to give 3′-monochloro and 3′,5′-dichloro products. Equilibrium constants for the transchlorination reactions: HOCl + HIm = H2O + ImCl and NH2Cl + HIm = NH3 + ImCl were estimated from the dependence of the rate constants upon [HIm]/[HOCl] and literature data. Acid catalysis again suggests that the actual chlorinating agent is HImCl+; consistent with this interpretation, MeIm markedly catalyzed fluorescein chlorination by HOCl. Time-dependent imidazole-catalyzed HPA chlorination by NH2Cl was also demonstrated by product analyses. Quantitative assessment of the data suggests that physiological levels of histidyl groups will react with primary chloramines to generate a flux of imidazole chloramine sufficient to catalyze biological chlorination via HImCl+, particularly in environments that generate high concentrations of HOCl such as the neutrophil phagosome. PMID:25660996

A new mild base-catalyzed Mannich reaction of hetero-arylamines in water: highly efficient stereoselective synthesis of beta-aminoketones under microwave heating.

PubMed

Hao, Wen-Juan; Jiang, Bo; Tu, Shu-Jiang; Cao, Xu-Dong; Wu, Shan-Shan; Yan, Shu; Zhang, Xiao-Hong; Han, Zheng-Guo; Shi, Feng

2009-04-07

A new mild base-catalyzed Mannich reaction of aromatic aldehydes with 1,2-diphenylethanone and hetero-arylamines including pyridin-2-amine and pyrimidin-2-amine is described. In this reaction, a series of new beta-aminoketones were stereoselectively synthesized in water by controlling the steric hindrance of the substrates under microwave heating. This method has the advantages of a short synthetic route, operational simplicity, increased safety for small-scale high-speed synthesis, and minimal environmental impact.

Structure-based Mechanism of CMP-2-keto-3-deoxymanno-octulonic Acid Synthetase

PubMed Central

Heyes, Derren J.; Levy, Colin; Lafite, Pierre; Roberts, Ian S.; Goldrick, Marie; Stachulski, Andrew V.; Rossington, Steven B.; Stanford, Deborah; Rigby, Stephen E. J.; Scrutton, Nigel S.; Leys, David

2009-01-01

The enzyme CMP-Kdo synthetase (KdsB) catalyzes the addition of 2-keto-3-deoxymanno-octulonic acid (Kdo) to CTP to form CMP-Kdo, a key reaction in the biosynthesis of lipopolysaccharide. The reaction catalyzed by KdsB and the related CMP-acylneuraminate synthase is unique among the sugar-activating enzymes in that the respective sugars are directly coupled to a cytosine monophosphate. Using inhibition studies, in combination with isothermal calorimetry, we show the substrate analogue 2β-deoxy-Kdo to be a potent competitive inhibitor. The ligand-free Escherichia coli KdsB and ternary complex KdsB-CTP-2β-deoxy-Kdo crystal structures reveal that Kdo binding leads to active site closure and repositioning of the CTP phosphates and associated Mg2+ ion (Mg-B). Both ligands occupy conformations compatible with an Sn2-type attack on the α-phosphate by the Kdo 2-hydroxyl group. Based on strong similarity with DNA/RNA polymerases, both in terms of overall chemistry catalyzed as well as active site configuration, we postulate a second Mg2+ ion (Mg-A) is bound by the catalytically competent KdsB-CTP-Kdo ternary complex. Modeling of this complex reveals the Mg-A coordinated to the conserved Asp100 and Asp235 in addition to the CTP α-phosphate and both the Kdo carboxylic and 2-hydroxyl groups. EPR measurements on the Mn2+-substituted ternary complex support this model. We propose the KdsB/CNS sugar-activating enzymes catalyze the formation of activated sugars, such as the abundant CMP-5-N-acetylneuraminic acid, by recruitment of two Mg2+ to the active site. Although each metal ion assists in correct positioning of the substrates and activation of the α-phosphate, Mg-A is responsible for activation of the sugar-hydroxyl group. PMID:19815542

Intramolecular Hydrogen Transfer Reactions Catalyzed by Pentamethylcyclopentadienyl Rhodium and Cobalt Olefin Complexes: Mechanistic Studies.

PubMed

Bolig, Andrew D; Lyons, Thomas W; DiSalvo, Darren T; Brookhart, Maurice

2016-01-08

The mechanism of intramolecular transfer dehydrogenation catalyzed by [Cp * M(VTMS) 2 ] ( 1 , M=Rh, 2 , M=Co, Cp* = C 5 Me 5 , VTMS = vinyltrimethylsilane) complexes has been studied using vinyl silane protected alcohols as substrates. Deuterium-labeled substrates have been synthesized and the regioselectivity of H/D transfers investigated using 1 H and 2 H NMR spectroscopy. The labeling studies establish a regioselective pathway consisting of alkene directed α C-H activation, 2,1 alkene insertion, and finally β-hydride elimination to give silyl enol ether products.

Nickel(0)-Catalyzed Inert C-O Bond Functionalization: Organo Rare-Earth Metal Complex as the Coupling Partner.

PubMed

Yan, Xiangqian; Yang, Fanzhi; Cai, Guilong; Meng, Qingwei; Li, Xiaofang

2018-02-02

An organo rare-earth metal complex has been employed as a highly efficient nucleophile in Ni(0)-catalyzed C-O bond functionalization. The optimized catalytic system which consists of Ni(cod) 2 , PCy 3 , and t-BuONa could smoothly convert 1 equiv of naphthyl ethers to alkylated naphthalene analogues with 0.4 equiv of Ln(CH 2 SiMe 3 ) 3 (THF) 2 , delivering good to excellent yields. The reaction system could also activate the ArCH 2 -O bond with mild base.

Triphenylphosphine as Ligand for Room Temperature Ni(0)-Catalyzed Cross-Coupling Reactions of Aryl Chlorides with Arylboronic Acids

PubMed Central

Tang, Zhen-Yu; Hu, Qiao-Sheng

2008-01-01

Room temperature Ni(0)-catalyzed cross-coupling reactions of deactivated aryl chlorides with arylboronic acids with inexpensive triphenylphosphine (PPh3) as a supporting ligand have been accomplished in good to excellent yields. Air-stable Ni(PPh3)2Cl2 has also been established as catalyst precursor and highly active nickel catalysts were obtained when the reduction of Ni(PPh3)2Cl2 with n-BuLi was carried out in presence of an aryl chloride. PMID:16497011

Rhodium(II)-Catalyzed and Thermally Induced Intramolecular Migration of N-Sulfonyl-1,2,3-triazoles: New Approaches to 1,2-Dihydroisoquinolines and 1-Indanones.

PubMed

Sun, Run; Jiang, Yu; Tang, Xiang-Ying; Shi, Min

2016-04-11

New rhodium(II)-catalyzed or thermally induced intramolecular alkoxy group migration of N-sulfonyl-1,2,3-triazoles has been developed, affording divergent synthesis of 1,2-dihydroisoquinoline and 1-indanone derivatives according to different conditions. N-Sulfonyl keteneimine is the key intermediate for the synthesis of dihydroisoquinoline, whereas the aza-vinyl carbene intermediate results in the formation of 1-indanone. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 2-Aryl- and 2-Vinylpyrrolidines via Copper-Catalyzed Coupling of Styrenes and Dienes with Potassium β-Aminoethyl Trifluoroborates.

PubMed

Um, Chanchamnan; Chemler, Sherry R

2016-05-20

2-Arylpyrrolidines occur frequently in bioactive compounds, and thus, methods to access them from readily available reagents are valuable. We report a copper-catalyzed intermolecular carboamination of vinylarenes with potassium N-carbamoyl-β-aminoethyltrifluoroborates. The reaction occurs with terminal, 1,2-disubstituted, and 1,1-disubstituted vinylarenes bearing a number of functional groups. 1,3-Dienes are also good substrates, and their reactions give 2-vinylpyrrolidines. Radical clock mechanistic experiments are consistent with the presence of carbon radical intermediates and do not support participation of carbocations.

Reactivity and Selectivity in Hydrovinylation of Strained Alkenes

PubMed Central

Liu, Wang; RajanBabu, T. V.

2010-01-01

Scope of Ni(II)-catalyzed hydrovinylation has been extended to strained alkenes such as heterobicyclic- [2.2.1]heptanes and cylobutenes. Reactions involving the heterobicyclic compounds are rare examples for this class of compounds where the metal-catalyzed C-C bond-forming reactions proceed without a concomitant ring-opening process. While the enantioselectivity in these systems remains modest, hydrovinylation of endo-5,6--bis-benzyloxymethylbicyclo[2.2.1]hept-2-ene gives excellent yield (>90%) of the product with one of the highest enantioselectivities (95–99 %ee) reported for a C-C bondforming reaction of norbornenes. PMID:20964350

Effects of metal salt catalysts on yeast cell growth in ethanol conversion

Treesearch

Chung-Yun Hse; Yin Lin

2009-01-01

The effects of the addition of metal salts and metal salt-catalyzed hydrolyzates on yeast cell growth in ethanol fermentation were investigated. Four yeast strains (Saccharomyces cerevisiae WT1, Saccharomyces cerevisiae MT81, Candida sp. 1779, and Klumaromyces fragilis), four metal salts (CuCl2, FeCl3, AgNO3, and I2), two metal salt-catalyzed hydrolyzates (...

Regioselective syntheses of 1,2-benzothiazines by rhodium-catalyzed annulation reactions.

PubMed

Cheng, Ying; Bolm, Carsten

2015-10-12

Rhodium-catalyzed directed carbene insertions into aromatic CH bonds of S-aryl sulfoximines lead to intermediates, which upon dehydration provide 1,2-benzothiazines in excellent yields. The domino-type process is regioselective and shows a high functional-group tolerance. It is scalable, and the only by-products are dinitrogen and water. Three illustrative transformations underscore the synthetic value of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Single and Double Dibenzohelicenes by Rhodium-Catalyzed Intramolecular [2+2+2] and [2+1+2+1] Cycloaddition.

PubMed

Yamano, Ryota; Shibata, Yu; Tanaka, Ken

2018-04-25

Dibenzo[7]helicenes were synthesized with up to 99 % ee by rhodium(I)/binap-catalyzed enantioselective intramolecular [2+2+2] cycloaddition of 2-phenylnaphthalene-linked triynes. Additionally, [2+1+2+1] cycloaddition products, that is, twisted anthracenes, were also synthesized by using difluorphos as ligand. Although these compounds are not configurationally stable at elevated temperature, their Scholl reactions afforded configurationally stable double dibenzo[6]helicenes. The thus-obtained dibenzo[7]helicene exhibited good circularly polarized luminescence property and the double dibenzo[6]helicene showed high fluorescence quantum yield. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of ortho-para ratio controlled D2 gas for muon-catalyzed fusion.

PubMed

Imao, H; Ishida, K; Kawamura, N; Matsuzaki, T; Matsuda, Y; Toyoda, A; Strasser, P; Iwasaki, M; Nagamine, K

2008-05-01

A negative muon in hydrogen targets, e.g., D2 or D-T mixture, can catalyze nuclear fusions following a series of atomic processes involving muonic hydrogen molecular formation (muon-catalyzed fusion, muCF). The ortho-para state of D2 is a crucial parameter not only for enhancing the fusion rate but also to precisely investigate various muonic atom processes. We have developed a system for controlling and measuring the ortho-para ratio of D2 gas for muCF experiments. We successfully collected para-enriched D2 without using liquid-hydrogen coolant. Ortho-enriched D2 was also obtained by using a catalytic conversion method with a mixture of chromium oxide and alumina. The ortho-para ratio of D2 gas was measured with a compact Raman spectroscopy system. We produced large volume (5-30 l at STP), high-purity (less than ppm high-Z contaminant) D2 targets with a wide range of ortho-para ratios (ortho 20%-99%). By using the ortho-para controlled D2 in muCF experiments, we observed the dependence of muCF phenomena on the ortho-para ratio.

Preparation of ortho-para ratio controlled D{sub 2} gas for muon-catalyzed fusion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imao, H.; Ishida, K.; Matsuzaki, T.

2008-05-15

A negative muon in hydrogen targets, e.g., D{sub 2} or D-T mixture, can catalyze nuclear fusions following a series of atomic processes involving muonic hydrogen molecular formation (muon-catalyzed fusion, {mu}CF). The ortho-para state of D{sub 2} is a crucial parameter not only for enhancing the fusion rate but also to precisely investigate various muonic atom processes. We have developed a system for controlling and measuring the ortho-para ratio of D{sub 2} gas for {mu}CF experiments. We successfully collected para-enriched D{sub 2} without using liquid-hydrogen coolant. Ortho-enriched D{sub 2} was also obtained by using a catalytic conversion method with a mixturemore » of chromium oxide and alumina. The ortho-para ratio of D{sub 2} gas was measured with a compact Raman spectroscopy system. We produced large volume (5-30 l at STP), high-purity (less than ppm high-Z contaminant) D{sub 2} targets with a wide range of ortho-para ratios (ortho 20%-99%). By using the ortho-para controlled D{sub 2} in {mu}CF experiments, we observed the dependence of {mu}CF phenomena on the ortho-para ratio.« less

Rapid Construction of Complex 2-Pyrrolines through Lewis Acid-Catalyzed, Sequential Three-Component Reactions via in Situ-Generated 1-Azaallyl Cations.

PubMed

Schlegel, Marcel; Schneider, Christoph

2018-05-09

The first Sc(OTf) 3 -catalyzed dehydration of 2-hydroxy oxime ethers to generate benzylic stabilized 1-azaallyl cations, which are captured by 1,3-carbonyls, is described. A subsequent addition of primary amines in a sequential three-component reaction affords highly substituted and densely functionalized tetrahydroindeno[2,1- b]pyrroles as single diastereomers with up to quantitative yield. Thus, three new σ-bonds and two vicinal quaternary stereogenic centers are generated in a one-pot operation.

Supercritical CO2 as a reaction medium for synthesis of capsaicin analogues by lipase-catalyzed transacylation of capsaicin.

PubMed

Kobata, Kenji; Kobayashi, Mamiko; Kinpara, Sachiyo; Watanabe, Tatsuo

2003-09-01

Capsaicin analogues having different acyl moiety were synthesized by lipase-catalyzed transacylation of capsaicin with a corresponding acyl donor in supercritical CO2 as a reaction medium. Transacylation with methyl tetradecanoate using Novozym 435 as a catalyst gave vanillyl tetradecanamide in a 54% yield at 80 degrees C and 19 MPa over 72 h. Vanillyl (Z)-9-octadecenamide, olvanil, was synthesized from triolein in a 21% yield over 7 d.

Effect of genetic polymorphism on the inhibition of dopamine formation from p-tyramine catalyzed by brain cytochrome P450 2D6.

PubMed

Niwa, Toshiro; Shizuku, Marina; Yamano, Kaori

2017-04-15

The inhibitory effects of steroid hormones, including glucocorticoids such as cortisol, and related compounds on dopamine formation from p-tyramine, catalyzed by cytochrome P450 (CYP) 2D6.2 (Arg296Cys, Ser486Thr) and CYP2D6.10 (Pro34Ser, Ser486Thr) were compared with the effects of those catalyzed by CYP2D6.1 (wild type), to investigate the effect of a CYP2D6 polymorphism on neuroactive amine metabolism in the brain. Inhibition constants (K i ) or 50% inhibitory concentrations of six steroid hormones (cortisol, cortisone, corticosterone, dehydroepiandrosterone, progesterone, and pregnenolone) and quinidine and quinine-typical potent inhibitors of the human CYP2D6 and rat CYP2D subfamily, respectively-toward dopamine formation catalyzed by CYP2D6.1, CYP2D6.2, and CYP2D6.10 expressed in recombinant Escherichia coli were compared. Although most steroid hormones had no or minor inhibitory effects on the dopamine formation by all CYP2D6 variants, progesterone inhibited the metabolism and K i value against CYP2D6.10 was approximately twice that for CYP2D6.1 and CYP2D6.2. Quinidine exhibited stronger inhibition than quinine; however, these two compounds inhibited the CYP2D6.10-mediated reaction more weakly than the CYP2D6.1 and CYP2D6.2 reactions. These results suggest that CYP2D6 polymorphism would affect drug interaction through dopamine formation in the brain. Copyright © 2017 Elsevier Inc. All rights reserved.

Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds.

PubMed

Wang, He; Tang, Guodong; Li, Xingwei

2015-10-26

Nitrogenation by direct functionalization of C-H bonds represents an important strategy for constructing C-N bonds. Rhodium(III)-catalyzed direct amidation of unactivated C(sp(3) )-H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp(3) )-H bonds are amidated under rhodium catalysis in high efficiency using 3-substituted 1,4,2-dioxazol-5-ones as the amide source. The protocol broadens the scope of rhodium(III)-catalyzed C(sp(3) )-H activation chemistry, and is applicable to the late-stage functionalization of natural products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rh-Catalyzed [3 + 2] Cycloaddition of 1-Sulfonyl-1,2,3-triazoles: Access to the Framework of Aspidosperma and Kopsia Indole Alkaloids.

PubMed

Li, Yun; Zhang, Qingyu; Du, Qiucheng; Zhai, Hongbin

2016-08-19

A Rh(II)-catalyzed dearomative intramolecular [3 + 2] dipolar cycloaddition involving the indolic C2-C3 carbon-carbon double bond has been developed. The reaction was launched from the triazole moiety within the substrate and proceeded efficiently under mild conditions. A wide range of functional groups could be tolerated. These features render the current reaction a highly useful tool for the synthesis of polycyclic indole alkaloids, as showcased by a rapid assembly of the core structure of Aspidosperma and the related alkaloids.

Intramolecular Benzoin Reaction Catalyzed by Benzaldehyde Lyase from Pseudomonas Fluorescens Biovar I.

PubMed

Hernández, Karel; Parella, Teodor; Petrillo, Giovanna; Usón, Isabel; Wandtke, Claudia M; Joglar, Jesús; Bujons, Jordi; Clapés, Pere

2017-05-02

Intramolecular benzoin reactions catalyzed by benzaldehyde lyase from Pseudomonas fluorescens biovar I (BAL) are reported. The structure of the substrates envisaged for this reaction consists of two benzaldehyde derivatives linked by an alkyl chain. The structural requirements needed to achieve the intramolecular carbon-carbon bond reaction catalyzed by BAL were established. Thus, a linker consisting of a linear alkyl chain of three carbon atoms connected through ether-type bonds to the 2 and 2' positions of two benzaldehyde moieties, which could be substituted with either Cl, Br, or OCH 3 at either the 3 and 3' or 5 and 5' positions, were suitable substrates for BAL. Reactions with 61-84 % yields of the intramolecular product and ee values between 64 and 98 %, were achieved. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Clostridium acidurici Electron-Bifurcating Formate Dehydrogenase

PubMed Central

Wang, Shuning; Huang, Haiyan; Kahnt, Jörg

2013-01-01

Cell extracts of uric acid-grown Clostridium acidurici catalyzed the coupled reduction of NAD+ and ferredoxin with formate at a specific activity of 1.3 U/mg. The enzyme complex catalyzing the electron-bifurcating reaction was purified 130-fold and found to be composed of four subunits encoded by the gene cluster hylCBA-fdhF2. PMID:23872566

Pd-catalyzed intramolecular oxidative C-H amination: synthesis of carbazoles.

PubMed

Youn, So Won; Bihn, Joon Hyung; Kim, Byung Seok

2011-07-15

A Pd-catalyzed oxidative C-H amination of N-Ts-2-arylanilines under ambient temperature using Oxone as an inexpensive, safe, and easy-to-handle oxidant has been developed. This process represents a green and practical method for the facile construction of carbazoles with a broad substrate scope and wide functional group tolerance. © 2011 American Chemical Society

Rhodium-Catalyzed Insertion Reaction of PhP Group of Pentaphenylcyclopentaphosphine with Acyclic and Cyclic Disulfides.

PubMed

Arisawa, Mieko; Sawahata, Kyosuke; Yamada, Tomoki; Sarkar, Debayan; Yamaguchi, Masahiko

2018-02-16

Organophosphorus compounds with a phosphorus atom attached to a phenyl group and two organothio/organoseleno groups were synthesized using the rhodium-catalyzed insertion reaction of the PhP group of pentaphenylcyclopentaphosphine (PhP) 5 with acyclic disulfides and diselenides. The method was applied to the synthesis of heterocyclic compounds containing the S-P-S group by the reaction of (PhP) 5 and cyclic disulfides such as 1,2-dithietes, 1,2-dithiocane, 1,4,5-dithiopane, and 1,2-dithiolanes.

Reconstitution of Saccharomyces cerevisiae DNA polymerase ε-dependent mismatch repair with purified proteins.

PubMed

Bowen, Nikki; Kolodner, Richard D

2017-04-04

Mammalian and Saccharomyces cerevisiae mismatch repair (MMR) proteins catalyze two MMR reactions in vitro. In one, mispair binding by either the MutS homolog 2 (Msh2)-MutS homolog 6 (Msh6) or the Msh2-MutS homolog 3 (Msh3) stimulates 5' to 3' excision by exonuclease 1 (Exo1) from a single-strand break 5' to the mispair, excising the mispair. In the other, Msh2-Msh6 or Msh2-Msh3 activate the MutL homolog 1 (Mlh1)-postmeiotic segregation 1 (Pms1) endonuclease in the presence of a mispair and a nick 3' to the mispair, to make nicks 5' to the mispair, allowing Exo1 to excise the mispair. DNA polymerase δ (Pol δ) is thought to catalyze DNA synthesis to fill in the gaps resulting from mispair excision. However, colocalization of the S. cerevisiae mispair recognition proteins with the replicative DNA polymerases during DNA replication has suggested that DNA polymerase ε (Pol ε) may also play a role in MMR. Here we describe the reconstitution of Pol ε-dependent MMR using S. cerevisiae proteins. A mixture of Msh2-Msh6 (or Msh2-Msh3), Exo1, RPA, RFC-Δ1N, PCNA, and Pol ε was found to catalyze both short-patch and long-patch 5' nick-directed MMR of a substrate containing a +1 (+T) mispair. When the substrate contained a nick 3' to the mispair, a mixture of Msh2-Msh6 (or Msh2-Msh3), Exo1, RPA, RFC-Δ1N, PCNA, and Pol ε was found to catalyze an MMR reaction that required Mlh1-Pms1. These results demonstrate that Pol ε can act in eukaryotic MMR in vitro.

3-Hydroxylaminophenol Mutase from Ralstonia eutropha JMP134 Catalyzes a Bamberger Rearrangement

PubMed Central

Schenzle, Andreas; Lenke, Hiltrud; Spain, Jim C.; Knackmuss, Hans-Joachim

1999-01-01

3-Hydroxylaminophenol mutase from Ralstonia eutropha JMP134 is involved in the degradative pathway of 3-nitrophenol, in which it catalyzes the conversion of 3-hydroxylaminophenol to aminohydroquinone. To show that the reaction was really catalyzed by a single enzyme without the release of intermediates, the corresponding protein was purified to apparent homogeneity from an extract of cells grown on 3-nitrophenol as the nitrogen source and succinate as the carbon and energy source. 3-Hydroxylaminophenol mutase appears to be a relatively hydrophobic but soluble and colorless protein consisting of a single 62-kDa polypeptide. The pI was determined to be at pH 4.5. In a database search, the NH2-terminal amino acid sequence of the undigested protein and of two internal sequences of 3-hydroxylaminophenol mutase were found to be most similar to those of glutamine synthetases from different species. Hydroxylaminobenzene, 4-hydroxylaminotoluene, and 2-chloro-5-hydroxylaminophenol, but not 4-hydroxylaminobenzoate, can also serve as substrates for the enzyme. The enzyme requires no oxygen or added cofactors for its reaction, which suggests an enzymatic mechanism analogous to the acid-catalyzed Bamberger rearrangement. PMID:10049374

Enantioselective synthesis of syn/anti-1,3-amino alcohols via proline-catalyzed sequential alpha-aminoxylation/alpha-amination and Horner-Wadsworth-Emmons olefination of aldehydes.

PubMed

Jha, Vishwajeet; Kondekar, Nagendra B; Kumar, Pradeep

2010-06-18

A novel and general method for asymmetric synthesis of both syn/anti-1,3-amino alcohols is described. The method uses proline-catalyzed sequential alpha-aminoxylation/ alpha-amination and Horner-Wadsworth-Emmons (HWE) olefination of aldehydes as the key step. By using this method, a short synthesis of a bioactive molecule, (R)-1-((S)-1-methylpyrrolidin-2-yl)-5-phenylpentan-2-ol, is also accomplished.

Rh(III)-Catalyzed C-H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[ de]chromenes.

PubMed

Fang, Feifei; Zhang, Chunmei; Zhou, Chaofan; Li, Yazhou; Zhou, Yu; Liu, Hong

2018-04-06

Rh (III)-catalyzed C-H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[ de]chromenes via a formal (4 + 2) cycloaddition with a diazo compound and subsequent tandem (4 + 2) cycloaddition with another diazo compound. Intriguingly, synthesis of substituted benzo[ de]chromenes and their decarboxylation products could be realized by controlling the reaction conditions. These reactions have a broad range of substrates, moderate to good yields, and high regioselectivity.

Ferrocene Derived Bifunctional Phosphine-Catalyzed Asymmetric Oxa-[4+2] Cycloaddition of α-Substituted Allenones with Enones.

PubMed

Wang, Huamin; Lu, Weike; Zhang, Junliang

2017-10-04

An efficient ferrocene-derived bifunctional phosphine-catalyzed enantioselective oxa-[4+2] cycloaddition of α-substituted allenones with a broad range of enones is investigated for the preparation of stereodefined dihydropyrans in good to excellent yields (up to 99 %) and excellent enantioselectivity (up to 99 % ee). Furthermore, a series of valuable chiral polyheterocyclic frameworks can be efficiently achieved in good yields with excellent enantioselectivities. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extended reaction scope of thiamine diphosphate dependent cyclohexane-1,2-dione hydrolase: from C-C bond cleavage to C-C bond ligation.

PubMed

Loschonsky, Sabrina; Wacker, Tobias; Waltzer, Simon; Giovannini, Pier Paolo; McLeish, Michael J; Andrade, Susana L A; Müller, Michael

2014-12-22

ThDP-dependent cyclohexane-1,2-dione hydrolase (CDH) catalyzes the CC bond cleavage of cyclohexane-1,2-dione to 6-oxohexanoate, and the asymmetric benzoin condensation between benzaldehyde and pyruvate. One of the two reactivities of CDH was selectively knocked down by mutation experiments. CDH-H28A is much less able to catalyze the CC bond formation, while the ability for CC bond cleavage is still intact. The double variant CDH-H28A/N484A shows the opposite behavior and catalyzes the addition of pyruvate to cyclohexane-1,2-dione, resulting in the formation of a tertiary alcohol. Several acyloins of tertiary alcohols are formed with 54-94 % enantiomeric excess. In addition to pyruvate, methyl pyruvate and butane-2,3-dione are alternative donor substrates for CC bond formation. Thus, the very rare aldehyde-ketone cross-benzoin reaction has been solved by design of an enzyme variant. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

PubMed Central

Driver, Tom G.

2011-01-01

Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

Iron-catalyzed cross-coupling of imidoyl chlorides with Grignard reagents.

PubMed

Ottesen, Lars K; Ek, Fredrik; Olsson, Roger

2006-04-27

[reaction: see text] A general, high yielding rapid iron-catalyzed cross-coupling reaction between Grignard reagents and imidoyl chlorides is described. These reactions are typically completed within 5 min, resulting in high yields of 71-96% using 5% iron catalyst in a THF-NMP solvent mixture. Functionalized imidoyl chlorides (e.g., R = CO(2)Me) gave excellent yields (89%).

Stereoselective Synthesis of Tetrasubstituted Furylalkenes via Gold-Catalyzed Cross-Coupling of Enynones with Diazo Compounds.

PubMed

Liu, Pei; Sun, Jiangtao

2017-07-07

A stereoselective, gold-catalyzed, cross-coupling reaction of enynones with diazo compounds has been developed, affording 2-alkenylfurans in moderate to good yields with excellent E-stereoselectivity. Upon using diazo compounds as nucleophiles to trap the in situ formed gold furyl carbene, this protocol provides a novel path toward the formation of unsymmetrical tetrasubstituted alkenes.

Piper-betle-shaped nano-S-catalyzed synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition: a greener "nanoparticle-catalyzed organic synthesis enhancement" approach.

PubMed

Das, Vijay K; Borah, Madhurjya; Thakur, Ashim J

2013-04-05

Nano-S prepared by an annealing process showed excellent catalytic activity for the synthesis of 1-amidoalkyl-2-naphthols under solvent-free reaction condition at 50 °C. The catalyst could be reused up to the fifth cycle without loss in its action. The green-ness of the present protocol was also measured using green metrics drawing its superiority.

Iron-catalyzed vinylogous aldol condensation of Biginelli products and its application toward pyrido[4,3-d]pyrimidinones.

PubMed

Zhang, Lianqiang; Zhang, Zhiguo; Liu, Qingfeng; Liu, Tongxin; Zhang, Guisheng

2014-03-07

A novel iron-catalyzed vinylogous aldol condensation of Biginelli products with aryl aldehydes has been developed for the syntheses of potential bioactive (E)-6-arylvinyl-dihydropyrimidin-2(1H)-ones. These materials are valuable synthetic precursors to drug-like pyrido[4,3-d]pyrimidine derivatives. The amide group at the 5-position of the dihydropyrimidin-2(1H)-ones played an important role in the vinylogous aldol condensation reaction.

Purification and Characterization of a Glycerol-Resistant CF0-CF1 and CF1-ATPase from the Halotolerant Alga Dunaliella bardawil1

PubMed Central

Finel, Moshe; Pick, Uri; Selman-Reimer, Susanne; Selman, Bruce R.

1984-01-01

The isolation of the chloroplast ATP synthase complex (CF0-CF1) and of CF1 from Dunaliella bardawil is described. The subunit structure of the D. bardawil ATPase differs from that of the spinach in that the D. bardawil α subunit migrates ahead of the β subunit and ε-migrates ahead of subunit II of CF0 when separated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The CF1 isolated from D. bardawil resembles the CF1 isolated from Chladmydomonas reinhardi in that a reversible, Mg2+-dependent ATPase is induced by selected organic solvents. Glycerol stimulates cyclic photophosphorylation catalyzed by D. bardawil thylakoid membranes but inhibits photophosphorylation catalyzed by spinach thylakoid membranes. Glycerol (20%) also stimulates the rate of ATP-Pi exchange catalyzed by D. bardawil CF0-CF1 proteoliposomes but inhibits the activity with the spinach enzyme. The ethanol-activated, Mg2+-ATPase of the D. bardawil CF1 is more resistant to glycerol inhibition than the octylglucoside-activated, Mg2+-ATPase of spinach CF1 or the ethanol-activated, Mg2+-dependent ATPase of the C. reinhardi CF1. Both cyclic photophosphorylation and ATP-Pi exchange catalyzed by D. bardawil CF0-CF1 are more sensitive to high concentrations of NaCl than is the spinach complex. Images Fig. 5 PMID:16663507

Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis.

PubMed

Wallace, Debra J; Sidda, Rachel L; Reamer, Robert A

2007-02-02

A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

Ubiquitination independent of E1 and E2 enzymes by bacterial effectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Jiazhang; Sheedlo, Michael J.; Yu, Kaiwen

Signaling by ubiquitination regulates virtually every cellular process in eukaryotes. Covalent attachment of ubiquitin to a substrate is catalyzed by the E1, E2 and E3 three-enzyme cascade 1, which links the C terminus of ubiquitin via an isopeptide bond mostly to the ε-amino group of a lysine of the substrate. Given the essential roles of ubiquitination in the regulation of the immune system, it is not surprising that the ubiquitination network is a common target for diverse infectious agents 2. For example, many bacterial pathogens exploit ubiquitin signaling using virulence factors that function as E3 ligases, deubiquitinases 3 or asmore » enzymes that directly attack ubiquitin 4. The bacterial pathogen Legionella pneumophila utilizes approximately 300 effectors that modulate diverse host processes to create a niche permissive for its replication in phagocytes 5. Here we demonstrate that members of the SidE effector family (SidEs) of L. pneumophila ubiquitinate multiple Rab small GTPases associated with the endoplasmic reticulum (ER). Moreover, we show that these proteins are capable of catalyzing ubiquitination without the need for the E1 and E2 enzymes. The E1/E2-independent ubiquitination catalyzed by these enzymes requires NAD but not ATP and Mg2+. A putative mono ADP-ribosyltransferase (mART) motif critical for the ubiquitination activity is also essential for the role of SidEs in intracellular bacterial replication in a protozoan host. These results establish that ubiquitination can be catalyzed by a single enzyme.« less

Kinetics of the Decomposition of Hydrogen Peroxide Catalyzed by Ferric Ethylenediaminetetraacetate Complex

PubMed Central

Walling, Cheves; Partch, Richard E.; Weil, Tomas

1975-01-01

Added substrates, acetone and t-butyl alcohol, strongly retard the decomposition of H2O2 brought about by ferric ethylenediaminetetraacetate (EDTA) at pH 8-9.5. Their relative effectiveness and the kinetic form of the retardation are consistent with their interruption of a hydroxyl radical chain that is propagated by HO· attack both upon H2O2 and on complexed and uncomplexed EDTA. Similar retardation is observed with decompositions catalyzed by ferric nitrilotriacetate and hemin, and it is proposed that such redox chains may be quite a general path for transition metal ion catalysis of H2O2 decomposition. PMID:16592209

Cox-2 inhibitory effects of naturally occurring and modified fatty acids.

PubMed

Ringbom, T; Huss, U; Stenholm , A; Flock, S; Skattebøl, L; Perera, P; Bohlin, L

2001-06-01

In the search for new cyclooxygenase-2 (COX-2) selective inhibitors, the inhibitory effects of naturally occurring fatty acids and some of their structural derivatives on COX-2-catalyzed prostaglandin biosynthesis were investigated. Among these fatty acids, linoleic acid (LA), alpha-linolenic acid (alpha-LNA), myristic acid, and palmitic acid were isolated from a CH(2)Cl(2) extract of the plant Plantago major by bioassay-guided fractionation. Inhibitory effects of other natural, structurally related fatty acids were also investigated: stearic acid, oleic acid, pentadecanoic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA). Further, the inhibitory effects of these compounds on COX-2- and COX-1-catalyzed prostaglandin biosynthesis was compared with the inhibition of some synthesized analogues of EPA and DHA with ether or thioether functions. The most potent COX-2-catalyzed prostaglandin biosynthesis inhibitor was all-(Z)-5-thia-8,11,14,17-eicosatetraenoic acid (2), followed by EPA, DHA, alpha-LNA, LA, (7E,11Z,14Z,17Z)-5-thiaeicosa-7,11,14,17-tetraenoic acid, all-(Z)-3-thia-6,9,12,15-octadecatetraenoic acid, and (5E,9Z,12Z,15Z,18Z)-3-oxaheneicosa-5,9,12,15,18-pentaenoic acid, with IC(50) values ranging from 3.9 to180 microM. The modified compound 2 and alpha-LNA were most selective toward COX-2, with COX-2/COX-1 ratios of 0.2 and 0.1, respectively. This study shows that several of the natural fatty acids as well as all of the semisynthetic thioether-containing fatty acids inhibited COX-2-catalyzed prostaglandin biosynthesis, where alpha-LNA and compound 2 showed selectivity toward COX-2.

Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations.

PubMed

Grimes, Kimberly D; Gupte, Amol; Aldrich, Courtney C

2010-05-01

We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the substituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp(3)) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3-triazoles derivatives.

Nickel-Catalyzed Highly Regioselective Hydrocyanation of Terminal Alkynes with Zn(CN)2 Using Water as the Hydrogen Source.

PubMed

Zhang, Xingjie; Xie, Xin; Liu, Yuanhong

2018-06-08

The first efficient and general nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN) 2 in the presence of water has been developed. The reaction provides a regioselective protocol for the synthesis of functionalized vinyl nitriles with a range of structural diversity under mild reaction conditions while obviating use of the volatile and hazardous reagent of HCN. Deuterium-labeling experiments confirmed the role of water as the hydrogen source in this hydrocyanation reaction.

Consecutive three-component synthesis of (hetero)arylated propargyl amides by chemoenzymatic aminolysis-Sonogashira coupling sequence.

PubMed

Hassan, Sidra; Ullrich, Anja; Müller, Thomas J J

2015-02-07

A novel chemoenzymatic three-component synthesis of (hetero)arylated propargyl amides in good yields based upon Novozyme® 435 (Candida antarctica lipase B (CAL-B)) catalyzed aminolysis of methyl carboxylates followed by Sonogashira coupling with (hetero)aryliodides in a consecutive one-pot fashion has been presented. This efficient methodology can be readily concatenated with a CuAAC (Cu catalyzed alkyne azide cycloaddition) as a third consecutive step to furnish 1,4-disubstituted 1,2,3-triazole ligated arylated propargyl amides. This one-pot process can be regarded as a transition metal catalyzed sequence that takes advantage of the copper source still present from the cross-coupling step.

On the stereochemical course of palladium-catalyzed cross-coupling of allylic silanolate salts with aromatic bromides.

PubMed

Denmark, Scott E; Werner, Nathan S

2010-03-17

The stereochemical course of palladium-catalyzed cross-coupling reactions of an enantioenriched, alpha-substituted, allylic silanolate salt with aromatic bromides has been investigated. The allylic silanolate salt was prepared in high geometrical (Z/E, 94:6) and high enantiomeric (94:6 er) purity by a copper-catalyzed S(N)2' reaction of a resolved allylic carbamate. Eight different aromatic bromides underwent cross-coupling with excellent constitutional site-selectivity and excellent stereospecificity. Stereochemical correlation established that the transmetalation event proceeds through a syn S(E)' mechanism which is interpreted in terms of an intramolecular delivery of the arylpalladium electrophile through a key intermediate that contains a discrete Si-O-Pd linkage.

Coupled Ferredoxin and Crotonyl Coenzyme A (CoA) Reduction with NADH Catalyzed by the Butyryl-CoA Dehydrogenase/Etf Complex from Clostridium kluyveri▿ †

PubMed Central

Li, Fuli; Hinderberger, Julia; Seedorf, Henning; Zhang, Jin; Buckel, Wolfgang; Thauer, Rudolf K.

2008-01-01

Cell extracts of butyrate-forming clostridia have been shown to catalyze acetyl-coenzyme A (acetyl-CoA)- and ferredoxin-dependent formation of H2 from NADH. It has been proposed that these bacteria contain an NADH:ferredoxin oxidoreductase which is allosterically regulated by acetyl-CoA. We report here that ferredoxin reduction with NADH in cell extracts from Clostridium kluyveri is catalyzed by the butyryl-CoA dehydrogenase/Etf complex and that the acetyl-CoA dependence previously observed is due to the fact that the cell extracts catalyze the reduction of acetyl-CoA with NADH via crotonyl-CoA to butyryl-CoA. The cytoplasmic butyryl-CoA dehydrogenase complex was purified and is shown to couple the endergonic reduction of ferredoxin (E0′ = −410 mV) with NADH (E0′ = −320 mV) to the exergonic reduction of crotonyl-CoA to butyryl-CoA (E0′ = −10 mV) with NADH. The stoichiometry of the fully coupled reaction is extrapolated to be as follows: 2 NADH + 1 oxidized ferredoxin + 1 crotonyl-CoA = 2 NAD+ + 1 ferredoxin reduced by two electrons + 1 butyryl-CoA. The implications of this finding for the energy metabolism of butyrate-forming anaerobes are discussed in the accompanying paper. PMID:17993531

Stability of Catalyzed Magnesium Hydride Nanocrystalline During Hydrogen Cycling. Part II: Microstructure Evolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Chengshang; Fang, Zhigang Zak; Bowman, Robert C.

2015-10-01

In Part I, the cyclic stabilities of the kinetics of catalyzed MgH2 systems including MgH2–TiH2, MgH2–TiMn2, and MgH2–VTiCr were investigated, showing stable kinetics at 300 °C but deteriorations of the hydrogenation kinetics at temperatures below 150 °C. The present Part II describes the characterization of uncycled and cycled catalyzed MgH2 by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) analysis. XRD analysis shows the crystallite sizes of the Mg and MgH2 significantly increased after the cycling. The mean crystallite sizes of the catalysts (TiH2 and VTiCr) increased moderately after the cycling. SEMmore » and TEM imaging were used to compare the microstructures of uncycled (as-milled) and cycled materials, revealing a drastic change of the microstructure after 100 cycles. In particular, results from energy-dispersive spectroscopy (EDS) mapping show that a change of distribution of the catalyst particles in the Mg and MgH2 phase occurred during the cycling.« less

Maturation of nitrogenase cofactor—the role of a class E radical SAM methyltransferase NifB

PubMed Central

Hu, Yilin; Ribbe, Markus W.

2016-01-01

Nitrogenase catalyzes the important reactions of N2-, CO- and CO2-reduction at its active cofactor site. Designated the M-cluster, this complex metallocofactor is assembled through the generation of a characteristic 8Fe-core prior to the insertion of Mo and homocitrate that completes the stoichiometry of the M-cluster. NifB catalyzes the critical step of radical SAM-dependent carbide insertion that occurs concomitant with the insertion a “9th” sulfur and the rearrangement/coupling of two 4Fe-clusters into a complete 8Fe-core of the M-cluster. Further categorization of a family of NifB proteins as a new class of radical SAM methyltransferases suggests a general function of these proteins in complex metallocofactor assembly and provides a new platform for unveiling unprecedented chemical reactions catalyzed by biological systems. PMID:26969410

DOE Office of Scientific and Technical Information (OSTI.GOV)

Imker,H.; Fedorov, A.; Fedorov, E.

D-Ribulose 1,5-bisphosphate carboxylase/oxygenase (RuBisCO), the most abundant enzyme, is the paradigm member of the recently recognized mechanistically diverse RuBisCO superfamily. The RuBisCO reaction is initiated by abstraction of the proton from C3 of the D-ribulose 1,5-bisphosphate substrate by a carbamate oxygen of carboxylated Lys 201 (spinach enzyme). Heterofunctional homologues of RuBisCO found in species of Bacilli catalyze the tautomerization ('enolization') of 2,3-diketo-5-methylthiopentane 1-phosphate (DK-MTP 1-P) in the methionine salvage pathway in which 5-methylthio-D-ribose (MTR) derived from 5'-methylthioadenosine is converted to methionine [Ashida, H., Saito, Y., Kojima, C., Kobayashi, K., Ogasawara, N., and Yokota, A. (2003) A functional link between RuBisCO-likemore » protein of Bacillus and photosynthetic RuBisCO, Science 302, 286-290]. The reaction catalyzed by this 'enolase' is accomplished by abstraction of a proton from C1 of the DK-MTP 1-P substrate to form the tautomerized product, a conjugated enol. Because the RuBisCO- and 'enolase'-catalyzed reactions differ in the regiochemistry of proton abstraction but are expected to share stabilization of an enolate anion intermediate by coordination to an active site Mg{sup 2+}, we sought to establish structure-function relationships for the 'enolase' reaction so that the structural basis for the functional diversity could be established. We determined the stereochemical course of the reaction catalyzed by the 'enolases' from Bacillus subtilis and Geobacillus kaustophilus. Using stereospecifically deuterated samples of an alternate substrate derived from D-ribose (5-OH group instead of the 5-methylthio group in MTR) as well as of the natural DK-MTP 1-P substrate, we determined that the 'enolase'-catalyzed reaction involves abstraction of the 1-proS proton. We also determined the structure of the activated 'enolase' from G. kaustophilus (carboxylated on Lys 173) liganded with Mg{sup 2+} and 2,3-diketohexane 1-phosphate, a stable alternate substrate. The stereospecificity of proton abstraction restricts the location of the general base to the N-terminal {alpha}+ {beta} domain instead of the C-terminal ({beta}/{alpha}){sub 8}-barrel domain that contains the carboxylated Lys 173. Lys 98 in the N-terminal domain, conserved in all 'enolases', is positioned to abstract the 1-proS proton. Consistent with this proposed function, the K98A mutant of the G. kaustophilus 'enolase' is unable to catalyze the 'enolase' reaction. Thus, we conclude that this functionally divergent member of the RuBisCO superfamily uses the same structural strategy as RuBisCO for stabilizing the enolate anion intermediate, i.e., coordination to an essential Mg{sup 2+}, but the proton abstraction is catalyzed by a different general base.« less

Evidence that a phosphorylated derivative of 5-oxoproline (5-OP) is an intermediate in the reaction catalyzed by 5-oxoprolinase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seddon, A.P.; Meister, A.

1986-05-01

5-oxo-L-proline + ATP + 2 H/sub 2/O ..-->.. L-Glutamate + ADP + P/sub i/ Pseudomonas putida 5-oxoprolinase consists of 2 protein components (A and B). A catalyzes 5-OP-dependent ATPase. B, which does not appear to interact with ATP or 5-OP, is required for catalysis of the complete reaction. Application of the isotope trapping method showed that 5-OP is converted stoichiometrically to an enzyme-bound form in a process requiring ATP and its cleavage. The overall reaction is not inhibited by high concentrations of borohydride. When the reaction catalyzed by A alone is carried out in the presence of 0.1-0.6 M KBH/submore » 4/ there is catalytic formation of proline. Studies with KB/sup 3/H/sub 4/ showed incorporation of /sup 3/H into proline. Proline formation is prevented by addition of B.« less

Application of a new amidophosphite ligand to Rh-catalyzed asymmetric hydrogenation of β-dehydroamino acid derivatives in supercritical carbon dioxide: activation effect of protic Co-solvents.

PubMed

Lyubimov, Sergey E; Rastorguev, Eugenie A; Davankov, Vadim A

2011-09-01

New chiral amidophosphite ligand was synthesized and tested in the Rh-catalyzed asymmetric hydrogenation of (Z)-β-(acylamino)acrylates in protic solvents and supercritical carbon dioxide (scCO(2) ) The catalytic performance is affected greatly by the acidity of the solvents. Better enantioselectivity (up to 88% ee) was achieved in scCO(2) containing 1,1,1,3,3,3-hexafluoro-2-propanol, compared to neat protic solvents. Copyright © 2011 Wiley-Liss, Inc.

Catalyzed formation of α,β-unsaturated ketones or aldehydes from propargylic acetates by a recoverable and recyclable nanocluster catalyst

NASA Astrophysics Data System (ADS)

Li, Man-Bo; Tian, Shi-Kai; Wu, Zhikun

2014-05-01

An active, recoverable, and recyclable nanocluster catalyst, Au25(SR)18-, has been developed to catalyze the formation of α,β-unsaturated ketones or aldehydes from propargylic acetates. The catalytic process has been proposed to be initialized by an SN2' addition of OH-. Moreover, a dramatic solvent effect was observed, for which a rational explanation was provided.An active, recoverable, and recyclable nanocluster catalyst, Au25(SR)18-, has been developed to catalyze the formation of α,β-unsaturated ketones or aldehydes from propargylic acetates. The catalytic process has been proposed to be initialized by an SN2' addition of OH-. Moreover, a dramatic solvent effect was observed, for which a rational explanation was provided. Electronic supplementary information (ESI) available: Experimental procedures, UV-Vis spectra and fluorescence spectra of catalysts, characterization data, and copies of MS spectra. See DOI: 10.1039/c4nr00658e

Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Key, Hanna M.; Dydio, Paweł; Liu, Zhennan

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. Here, we postulated that the same type of Ir(Me)-PIX enzymes could catalyze the cyclopropanation of a broad range of alkenes with control of multiplemore » 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. Altogether, the studies reveal the suitability of Ir-containing P450s to combine the broad reactivity and substrate scope of transition metal catalysts with the exquisite selectivity of enzymes, generating catalysts that enable reactions to occur with levels and modes of activity and selectivity previously unattainable with natural enzymes or transition metal complexes alone.« less

Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes

DOE PAGES

Key, Hanna M.; Dydio, Paweł; Liu, Zhennan; ...

2017-04-01

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. Here, we postulated that the same type of Ir(Me)-PIX enzymes could catalyze the cyclopropanation of a broad range of alkenes with control of multiplemore » 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. Altogether, the studies reveal the suitability of Ir-containing P450s to combine the broad reactivity and substrate scope of transition metal catalysts with the exquisite selectivity of enzymes, generating catalysts that enable reactions to occur with levels and modes of activity and selectivity previously unattainable with natural enzymes or transition metal complexes alone.« less

Stringency of the 2-His–1-Asp Active-Site Motif in Prolyl 4-Hydroxylase

PubMed Central

Gorres, Kelly L.; Pua, Khian Hong; Raines, Ronald T.

2009-01-01

The non-heme iron(II) dioxygenase family of enzymes contain a common 2-His–1-carboxylate iron-binding motif. These enzymes catalyze a wide variety of oxidative reactions, such as the hydroxylation of aliphatic C–H bonds. Prolyl 4-hydroxylase (P4H) is an α-ketoglutarate-dependent iron(II) dioxygenase that catalyzes the post-translational hydroxylation of proline residues in protocollagen strands, stabilizing the ensuing triple helix. Human P4H residues His412, Asp414, and His483 have been identified as an iron-coordinating 2-His–1-carboxylate motif. Enzymes that catalyze oxidative halogenation do so by a mechanism similar to that of P4H. These halogenases retain the active-site histidine residues, but the carboxylate ligand is replaced with a halide ion. We replaced Asp414 of P4H with alanine (to mimic the active site of a halogenase) and with glycine. These substitutions do not, however, convert P4H into a halogenase. Moreover, the hydroxylase activity of D414A P4H cannot be rescued with small molecules. In addition, rearranging the two His and one Asp residues in the active site eliminates hydroxylase activity. Our results demonstrate a high stringency for the iron-binding residues in the P4H active site. We conclude that P4H, which catalyzes an especially demanding chemical transformation, is recalcitrant to change. PMID:19890397

Old Yellow Enzyme: Stepwise reduction of nitro-olefins and catalysis of aci-nitro tautomerization

PubMed Central

Meah, Younus; Massey, Vincent

2000-01-01

The Old Yellow Enzyme has been shown to catalyze efficiently the NADPH-linked reduction of nitro-olefins. The reduction of the nitro-olefin proceeds in a stepwise fashion, with formation of a nitronate intermediate that is freely dissociable from the enzyme. The first step involves hydride transfer from the enzyme-reduced flavin to carbon 2 of the nitro-olefin. The protonation of the nitronate at carbon 1 to form the final nitroalkane product also is catalyzed by the enzyme and involves Tyr-196 as an active site acid/base. This residue also is involved in aci-nitro tautomerization of nitroalkanes, the first example of a nonredox reaction catalyzed by the enzyme. PMID:10995477

Investigating lignin key features in maize lignocelluloses using infrared spectroscopy.

PubMed

Chazal, Richard; Robert, Paul; Durand, Sylvie; Devaux, Marie-Françoise; Saulnier, Luc; Lapierre, Catherine; Guillon, Fabienne

2014-01-01

Lignins and their cross-linking to hemicelluloses detrimentally affect the cellulose-to-ethanol conversion of grass lignocelluloses. Screening appropriate grass cell walls and their compositional changes during the various steps of the process calls for a high-throughput analytical technique. Such a performance can be fulfilled by Fourier transform mid-infrared (FT-MIR) spectroscopy. In the present paper, a set of maize cell walls from mature stems were selected, including brown midrib samples. Lignin fractions were isolated by mild acidolysis to obtain a set of purified maize lignin standards. The lignin content and the percentage of lignin-derived p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) thioacidolysis monomers were determined. In addition, the composition of cell wall polysaccharides, as well as the amount of ester-linked p-coumaric (CA) and ferulic (FA) acids, was measured by wet chemistry. Partial least square (PLS) analyses were applied to infrared and chemical data of cell walls. The resulting models showed a good predictive ability with regard to the lignin content, to the frequency of S (or G) thioacidolysis monomers, and to the level of ester-linked CA of maize cell walls. The loading plots and regression coefficients revealed relevant infrared absorption bands.

Electrochemical synthesis of formic acid from CO2 catalyzed by Shewanella oneidensis MR-1 whole-cell biocatalyst.

PubMed

Le, Quang Anh Tuan; Kim, Hee Gon; Kim, Yong Hwan

2018-09-01

The electro-biocatalytic conversion of CO 2 into formic acid using whole-cell and isolated biocatalysts is useful as an alternative route for CO 2 sequestration. In this study, Shewanella oneidensis MR-1 (S. oneidensis MR-1), a facultative aerobic bacterium that has been extensively studied for its utility as biofuel cells as well as for the detoxification of heavy metal oxides (i.e., MnO 2 , uranium), has been applied for the first time as a whole-cell biocatalyst for formic acid synthesis from gaseous CO 2 and electrons supplied from an electrode. S. oneidensis MR-1, when aerobically grown in Luria-Bertani (LB) medium, exhibited its ability as a whole-cell biocatalyst for the conversion of CO 2 into formic acid with moderate productivity of 0.59 mM h -1 for 24 h. In addition, an optimization of growth conditions of S. oneidensis MR-1 resulted in a remarkable increase in productivity. The CO 2 reduction reaction catalyzed by S. oneidensis MR-1, when anaerobically grown in newly optimized LB medium supplemented with fumarate and nitrate, exhibited 3.2-fold higher productivity (1.9 mM h -1 for 72 h) compared to that grown aerobically in only LB medium. Furthermore, the average conversion rate of formic acid synthesis catalyzed by S. oneidensis MR-1 when grown in the optimal medium over a period of 72 h was 3.8 mM h -1  g -1 wet-cell, which is 9.6-fold higher than that catalyzed by Methylobacterium extorquens AM1 whole-cells in our previous study. Copyright © 2018 Elsevier Inc. All rights reserved.

Pd-Catalyzed Acetoxylation of γ-C(sp3)-H Bonds of Amines Directed by a Removable Bts-Protecting Group.

PubMed

Zheng, Yong; Song, Weibin; Zhu, Yefu; Wei, Bole; Xuan, Lijiang

2018-02-16

Pd-catalyzed acetoxylation of γ-C(sp 3 )-H bonds directed by Bts-protected amines using inexpensive PhI(OAc) 2 as oxidant is reported. The Bts-protecting group is easily introduced and removed under mild conditions. This protocol provides an important strategy for the construction of γ-hydroxyl amine derivatives.

Mechanistic insights into iron catalyzed dehydrogenation of formic acid: β-hydride elimination vs. direct hydride transfer.

PubMed

Yang, Xinzheng

2013-09-07

Density functional theory calculations reveal a complete reaction mechanism with detailed energy profiles and transition state structures for the dehydrogenation of formic acid catalyzed by an iron complex, [P(CH2CH2PPh2)3FeH](+). In the cationic reaction pathway, a β-hydride elimination process is confirmed to be the rate-determining step in this catalytic reaction. A potential reaction pathway starting with a direct hydride transfer from HCOO(-) to Fe is found to be possible, but slightly less favorable than the catalytic cycle with a β-hydride elimination step.

Electrophilic assistance to the cleavage of an RNA model phopshodiester via specific and general base-catalyzed mechanisms.

PubMed

Corona-Martínez, David Octavio; Gomez-Tagle, Paola; Yatsimirsky, Anatoly K

2012-10-19

Kinetics of transesterification of the RNA model substrate 2-hydroxypropyl 4-nitrophenyl phosphate promoted by Mg(2+) and Ca(2+), the most common biological metals acting as cofactors for nuclease enzymes and ribozymes, as well as by Co(NH(3))(6)(3+), Co(en)(3)(3+), Li(+), and Na(+) cations, often employed as mechanistic probes, was studied in 80% v/v (50 mol %) aqueous DMSO, a medium that allows one to discriminate easily specific base (OH(-)-catalyzed) and general base (buffer-catalyzed) reaction paths. All cations assist the specific base reaction, but only Mg(2+) and Na(+) assist the general base reaction. For Mg(2+)-assisted reactions, the solvent deuterium isotope effects are 1.23 and 0.25 for general base and specific base mechanisms, respectively. Rate constants for Mg(2+)-assisted general base reactions measured with different bases fit the Brønsted correlation with a slope of 0.38, significantly lower than the slope for the unassisted general base reaction (0.77). Transition state binding constants for catalysts in the specific base reaction (K(‡)(OH)) both in aqueous DMSO and pure water correlate with their binding constants to 4-nitrophenyl phosphate dianion (K(NPP)) used as a minimalist transition state model. It was found that K(‡)(OH) ≈ K(NPP) for "protic" catalysts (Co(NH(3))(6)(3+), Co(en)(3)(3+), guanidinium), but K(‡)(OH) ≫ K(NPP) for Mg(2+) and Ca(2+) acting as Lewis acids. It appears from results of this study that Mg(2+) is unique in its ability to assist efficiently the general base-catalyzed transesterification often occurring in active sites of nuclease enzymes and ribozymes.

Theoretical studies on the Mo-catalyzed asymmetric intramolecular Pauson-Khand-type [2+2+1] cycloadditions of 3-allyloxy-1-propynylphosphonates.

PubMed

Meng, Qingxi; Li, Ming

2012-08-01

Density functional theory (DFT) was used to investigate the Mo-catalyzed intramolecular Pauson-Khand reaction of 3-allyloxy-1-propynylphosphonates. All intermediates and transition states were optimized completely at the B3LYP/6-31 G(d,p) level [LANL2DZ(f) for Mo]. In the Mo-catalyzed intramolecular Pauson-Khand reaction, the C–C oxidative cyclization reaction was the chirality-determining step, and the reductive elimination reaction was the rate-determining step. The carbonyl insertion reaction into the Mo–C(sp(3)) bondwas easier than into the Mo–C=C bond. And the dominant product predicted theoretically was of (S)-chirality, which agreed with experimental data. This reaction was solventd ependent, and toluene was the best among the three solvents toluene, CH3CN, and THF.

The divergent synthesis of nitrogen heterocycles by rhodium(II)-catalyzed cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes.

PubMed

Shang, Hai; Wang, Yuanhao; Tian, Yu; Feng, Juan; Tang, Yefeng

2014-05-26

The first rhodium(II)-catalyzed aza-[4+3] cycloadditions of 1-sulfonyl 1,2,3-triazoles with 1,3-dienes have been developed, and enable the efficient synthesis of highly functionalized 2,5-dihydroazepines from readily available precursors. In some cases, the reaction pathway could divert to formal aza-[3+2] cycloadditions, thus leading to 2,3-dihydropyrroles. In this context, the titled reaction represents a capable tool for the divergent synthesis of two types of synthetically valuable aza-heterocycles from common rhodium(II) iminocarbene intermediates. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evolution of Enzymatic Activities in the Enolase Superfamily: D-Tartrate Dehydratase from Bradyrhizobium japonicum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yew,W.; Fedorov, A.; Fedorov, E.

2006-01-01

We focus on the assignment of function to and elucidation of structure-function relationships for a member of the mechanistically diverse enolase superfamily encoded by the Bradyrhizobium japonicum genome (bll6730; GI:27381841). As suggested by sequence alignments, the active site contains the same functional groups found in the active site of mandelate racemase (MR) that catalyzes a 1,1-proton transfer reaction: two acid/base catalysts, Lys 184 at the end of the second {beta}-strand, and a His 322-Asp 292 dyad at the ends of the seventh and sixth -strands, respectively, as well as ligands for an essential Mg{sup 2+}, Asp 213, Glu 239, andmore » Glu 265 at the ends of the third, fourth, and fifth {beta}-strands, respectively. We screened a library of 46 acid sugars and discovered that only D-tartrate is dehydrated, yielding oxaloacetate as product. The kinetic constants (k{sub cat} = 7.3 s{sup -1}; k{sub cat}/K{sub M} = 8.5 x 10{sup 4} M{sup -1} s{sup -1}) are consistent with assignment of the D-tartrate dehydratase (TarD) function. The kinetic phenotypes of mutants as well as the structures of liganded complexes are consistent with a mechanism in which Lys 184 initiates the reaction by abstraction of the {alpha}-proton to generate a Mg{sup 2+}-stabilized enediolate intermediate, and the vinylogous -elimination of the 3-OH group is general acid-catalyzed by the His 322, accomplishing the anti-elimination of water. The replacement of the leaving group by solvent-derived hydrogen is stereorandom, suggesting that the enol tautomer of oxaloacetate is the product; this expectation was confirmed by its observation by {sup 1}H NMR spectroscopy. Thus, the TarD-catalyzed reaction is a 'simple' extension of the two-step reaction catalyzed by MR: base-catalyzed proton abstraction to generate a Mg{sup 2+}-stabilized enediolate intermediate followed by acid-catalyzed decomposition of that intermediate to yield the product.« less

Gold-Catalyzed Solid-Phase Synthesis of 3,4-Dihydropyrazin-2(1H)-ones: Relevant Pharmacophores and Peptide Backbone Constraints.

PubMed

Přibylka, Adam; Krchňák, Viktor

2017-11-13

Here, we report the efficient solid-phase synthesis of N-propargyl peptides using Fmoc-amino acids and propargyl alcohol as key building blocks. Gold-catalyzed nucleophilic addition to the triple bond induced C-N bond formation, which triggered intramolecular cyclization, yielding 1,3,4-trisubstituted-5-methyl-3,4-dihydropyrazin-2(1H)-ones. Conformations of acyclic and constrained peptides were compared using a two-step conformer distribution analysis at the molecular mechanics level and density functional theory. The results indicated that the incorporation of heterocyclic molecular scaffold into a short peptide sequence adopted extended conformation of peptide chain. The amide bond adjacent to the constraint did not show significant preference for either cis or trans isomerism. Prepared model compounds demonstrate a proof of concept for gold-catalyzed polymer-supported synthesis of variously substituted 3,4-dihydropyrazin-2(1H)-ones for applications in drug discovery and peptide backbone constraints.

Computation and Experiment: A Powerful Combination to Understand and Predict Reactivities.

PubMed

Sperger, Theresa; Sanhueza, Italo A; Schoenebeck, Franziska

2016-06-21

Computational chemistry has become an established tool for the study of the origins of chemical phenomena and examination of molecular properties. Because of major advances in theory, hardware and software, calculations of molecular processes can nowadays be done with reasonable accuracy on a time-scale that is competitive or even faster than experiments. This overview will highlight broad applications of computational chemistry in the study of organic and organometallic reactivities, including catalytic (NHC-, Cu-, Pd-, Ni-catalyzed) and noncatalytic examples of relevance to organic synthesis. The selected examples showcase the ability of computational chemistry to rationalize and also predict reactivities of broad significance. A particular emphasis is placed on the synergistic interplay of computations and experiments. It is discussed how this approach allows one to (i) gain greater insight than the isolated techniques, (ii) inspire novel chemistry avenues, and (iii) assist in reaction development. Examples of successful rationalizations of reactivities are discussed, including the elucidation of mechanistic features (radical versus polar) and origins of stereoselectivity in NHC-catalyzed reactions as well as the rationalization of ligand effects on ligation states and selectivity in Pd- and Ni-catalyzed transformations. Beyond explaining, the synergistic interplay of computation and experiments is then discussed, showcasing the identification of the likely catalytically active species as a function of ligand, additive, and solvent in Pd-catalyzed cross-coupling reactions. These may vary between mono- or bisphosphine-bound or even anionic Pd complexes in polar media in the presence of coordinating additives. These fundamental studies also inspired avenues in catalysis via dinuclear Pd(I) cycles. Detailed mechanistic studies supporting the direct reactivity of Pd(I)-Pd(I) with aryl halides as well as applications of air-stable dinuclear Pd(I) catalysts are discussed. Additional combined experimental and computational studies are described for alternative metals, these include the discussion of the factors that control C-H versus C-C activation in the aerobic Cu-catalyzed oxidation of ketones, and ligand and additive effects on the nature and favored oxidation state of the active catalyst in Ni-catalyzed trifluoromethylthiolations of aryl chlorides. Examples of successful computational reactivity predictions along with experimental verifications are then presented. This includes the design of a fluorinated ligand [(CF3)2P(CH2)2P(CF3)2] for the challenging reductive elimination of ArCF3 from Pd(II) as well as the guidance of substrate scope (functional group tolerance and suitable leaving group) in the Ni-catalyzed trifluoromethylthiolation of C(sp(2))-O bonds. In summary, this account aims to convey the benefits of integrating computational studies in experimental research to increase understanding of observed phenomena and guide future experiments.

Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

PubMed

Nash, Aaron; Soheili, Arash; Tambar, Uttam K

2013-09-20

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

Crystallographic and mutational analyses of cystathionine β-synthase in the H2 S-synthetic gene cluster in Lactobacillus plantarum.

PubMed

Matoba, Yasuyuki; Yoshida, Tomoki; Izuhara-Kihara, Hisae; Noda, Masafumi; Sugiyama, Masanori

2017-04-01

Cystathionine β-synthase (CBS) catalyzes the formation of l-cystathionine from l-serine and l-homocysteine. The resulting l-cystathionine is decomposed into l-cysteine, ammonia, and α-ketobutylic acid by cystathionine γ-lyase (CGL). This reverse transsulfuration pathway, which is catalyzed by both enzymes, mainly occurs in eukaryotic cells. The eukaryotic CBS and CGL have recently been recognized as major physiological enzymes for the generation of hydrogen sulfide (H 2 S). In some bacteria, including the plant-derived lactic acid bacterium Lactobacillus plantarum, the CBS- and CGL-encoding genes form a cluster in their genomes. Inactivation of these enzymes has been reported to suppress H 2 S production in bacteria; interestingly, it has been shown that H 2 S suppression increases their susceptibility to various antibiotics. In the present study, we characterized the enzymatic properties of the L. plantarum CBS, whose amino acid sequence displays a similarity with those of O-acetyl-l-serine sulfhydrylase (OASS) that catalyzes the generation of l-cysteine from O-acetyl-l-serine (l-OAS) and H 2 S. The L. plantarum CBS shows l-OAS- and l-cysteine-dependent CBS activities together with OASS activity. Especially, it catalyzes the formation of H 2 S in the presence of l-cysteine and l-homocysteine, together with the formation of l-cystathionine. The high affinity toward l-cysteine as a first substrate and tendency to use l-homocysteine as a second substrate might be associated with its enzymatic ability to generate H 2 S. Crystallographic and mutational analyses of CBS indicate that the Ala70 and Glu223 residues at the substrate binding pocket are important for the H 2 S-generating activity. © 2017 The Protein Society.

Copper catalyzed oxidative homocoupling of terminal alkynes to 1,3-diynes: a Cu3(BTC)2 MOF as an efficient and ligand free catalyst for Glaser-Hay coupling.

PubMed

Devarajan, Nainamalai; Karthik, Murugan; Suresh, Palaniswamy

2017-11-07

A straightforward and efficient method has been demonstrated for the oxidative coupling of terminal alkynes using a simple Cu 3 (BTC) 2 -metal organic framework as a sustainable heterogeneous copper catalyst. A series of symmetrical 1,3-diynes bearing diverse functional groups have been synthesized in moderate to excellent yields via a Cu 3 (BTC) 2 catalyzed Glaser-Hay reaction. The presence of the coordinatively unsaturated open Cu II sites in Cu 3 (BTC) 2 catalyzes the homocoupling in the presence of air, as an environment friendly oxidant without the use of external oxidants, ligands or any additives. The present methodology avoids stoichiometric reagents and harsher or special reaction conditions, and shows good functional group tolerance. The as-prepared catalyst could be separated easily by simple filtration and reused several times without any notable loss in activity. The hot filtration test has investigated the true heterogeneity of the catalyst. Additionally, the powder X-ray diffraction pattern of the reused catalyst revealed the high stability of the catalyst.

Unexpected regio- and chemoselectivity of cationic gold-catalyzed cycloisomerizations of propargylureas: access to tetrasubstituted 3,4-dihydropyrimidin-2(1H)-ones.

PubMed

Pereshivko, Olga P; Peshkov, Vsevolod A; Peshkov, Anatoly A; Jacobs, Jeroen; Van Meervelt, Luc; Van der Eycken, Erik V

2014-03-21

Cationic gold-catalyzed cycloisomerizations of propargylureas, derived in situ from secondary propargylamines and aryl or alkyl isocyanates, have been studied. The reaction outcome was found to be different from what was previously observed for the tosyl isocyanate-derived ureas in terms of both regio- and chemoselectivity. As a result, the current protocol offers efficient access to the 3,4-dihydropyrimidin-2(1H)-one core through the 6-endo-dig N-cyclization.

Synthesis of Imidazopyridines via Copper-Catalyzed, Formal Aza-[3 + 2] Cycloaddition Reaction of Pyridine Derivatives with α-Diazo Oxime Ethers.

PubMed

Park, Sangjune; Kim, Hyunseok; Son, Jeong-Yu; Um, Kyusik; Lee, Sooho; Baek, Yonghyeon; Seo, Boram; Lee, Phil Ho

2017-10-06

The Cu-catalyzed, formal aza-[3 + 2] cycloaddition reaction of pyridine derivatives with α-diazo oxime ethers in trifluoroethanol was used to synthesize imidazopyridines via the release of molecular nitrogen and elimination of alcohol. These methods enabled modular synthesis of a wide range of N-heterobicyclic compounds such as imidazopyridazines, imidazopyrimidines, and imidazopyrazines with an α-imino Cu-carbenoid generated from the α-diazo oxime ethers and copper.

Novel syn intramolecular pathway in base-catalyzed 1,2-elimination reactions of beta-acetoxy esters.

PubMed

Mohrig, Jerry R; Carlson, Hans K; Coughlin, Jane M; Hofmeister, Gretchen E; McMartin, Lea A; Rowley, Elizabeth G; Trimmer, Elizabeth E; Wild, Andrew J; Schultz, Steve C

2007-02-02

As part of a comprehensive investigation of electronic effects on the stereochemistry of base-catalyzed 1,2-elimination reactions, we observed a new syn intramolecular pathway in the elimination of acetic acid from beta-acetoxy esters and thioesters. 1H and 2H NMR investigation of reactions using stereospecifically labeled tert-butyl (2R*,3R*)-3-acetoxy-2,3-2H2-butanoate (1) and its (2R*,3S*) diastereomer (2) shows that 23 +/- 2% syn elimination occurs. The elimination reactions were catalyzed with KOH or (CH3)4NOH in ethanol/water under rigorously non-ion-pairing conditions. By contrast, the more sterically hindered beta-trimethylacetoxy ester produces only 6 +/- 1% syn elimination. These data strongly support an intramolecular (Ei) syn path for elimination of acetic acid, most likely through the oxyanion produced by nucleophilic attack at the carbonyl carbon of the beta-acetoxy group. The analogous thioesters, S-tert-butyl (2R*,3R*)-3-acetoxy-2,3-2H2-butanethioate (3) and its (2R*,3S*) diastereomer (4), showed 18 +/- 2% syn elimination, whereas the beta-trimethylacetoxy substrate gave 5 +/- 1% syn elimination. The more acidic thioester substrates do not produce an increased amount of syn stereoselectivity even though their elimination reactions are at the E1cb interface.

Enzyme Architecture: Self-Assembly of Enzyme and Substrate Pieces of Glycerol-3-Phosphate Dehydrogenase into a Robust Catalyst of Hydride Transfer.

PubMed

Reyes, Archie C; Amyes, Tina L; Richard, John P

2016-11-23

The stabilization of the transition state for hlGPDH-catalyzed reduction of DHAP due to the action of the phosphodianion of DHAP and the cationic side chain of R269 is between 12.4 and 17 kcal/mol. The R269A mutation of glycerol-3-phosphate dehydrogenase (hlGPDH) results in a 9.1 kcal/mol destabilization of the transition state for enzyme-catalyzed reduction of dihydroxyacetone phosphate (DHAP) by NADH, and there is a 6.7 kcal/mol stabilization of this transition state by 1.0 M guanidine cation (Gua + ) [J. Am. Chem. Soc. 2015, 137, 5312-5315]. The R269A mutant shows no detectable activity toward reduction of glycolaldehyde (GA), or activation of this reaction by 30 mM HPO 3 2- . We report the unprecedented self-assembly of R269A hlGPDH, dianions (X 2- = FPO 3 2- , HPO 3 2- , or SO 4 2- ), Gua + and GA into a functioning catalyst of the reduction of GA, and fourth-order reaction rate constants k cat /K GA K X K Gua . The linear logarithmic correlation (slope = 1.0) between values of k cat /K GA K X for dianion activation of wildtype hlGPDH-catalyzed reduction of GA and k cat /K GA K X K Gua shows that the electrostatic interaction between exogenous dianions and the side chain of R269 is not significantly perturbed by cutting hlGPDH into R269A and Gua + pieces. The advantage for connection of hlGPDH (R269A mutant + Gua + ) and substrate pieces (GA + HP i ) pieces, (ΔG S ‡ ) HPi+E+Gua = 5.6 kcal/mol, is nearly equal to the sum of the advantage to connection of the substrate pieces, (ΔG S ‡ ) GA+HPi = 3.3 kcal/mol, for wildtype hlGPDH-catalyzed reaction of GA + HP i , and for connection of the enzyme pieces, (ΔG S ‡ ) E+Gua = 2.4 kcal/mol, for Gua + activation of the R269A hlGPDH-catalyzed reaction of DHAP.

Palladium-catalyzed Kumada coupling reaction of bromoporphyrins with silylmethyl Grignard reagents: preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems.

PubMed

Sugita, Noriaki; Hayashi, Satoshi; Hino, Fumio; Takanami, Toshikatsu

2012-12-07

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH(2)OH, CH(2)OMe, and CH(2)F functionalities and the fluoride ion-mediated desilylative introduction of carbon-carbon single and double bonds.

Copper-catalyzed aerobic oxidative N-S bond functionalization for C-S bond formation: regio- and stereoselective synthesis of sulfones and thioethers.

PubMed

Li, Xianwei; Xu, Yanli; Wu, Wanqing; Jiang, Chang; Qi, Chaorong; Jiang, Huanfeng

2014-06-23

A regio- and stereoselective synthesis of sulfones and thioethers by means of Cu(I)-catalyzed aerobic oxidative N-S bond cleavage of sulfonyl hydrazides, followed by cross-coupling reactions with alkenes and aromatic compounds to form the C sp 2-S bond, is described herein. N2 and H2O are the byproducts of this transformation, thus offering an environmentally benign process with a wide range of potential applications in organic synthesis and medicinal chemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Site-specific recombination in the cyanobacterium Anabaena sp. strain PCC 7120 catalyzed by the integrase of coliphage HK022.

PubMed

Melnikov, Olga; Zaritsky, Arieh; Zarka, Aliza; Boussiba, Sammy; Malchin, Natalia; Yagil, Ezra; Kolot, Mikhail

2009-07-01

The integrase (Int) of the lambda-like coliphage HK022 catalyzes the site-specific integration and excision of the phage DNA into and from the chromosome of its host, Escherichia coli. Int recognizes two different pairs of recombining sites attP x attB and attL x attR for integration and excision, respectively. This system was adapted to the cyanobacterium Anabaena sp. strain PCC 7120 as a potential tool for site-specific gene manipulations in the cyanobacterium. Two plasmids were consecutively cointroduced by conjugation into Anabaena cells, one plasmid that expresses HK022 Int recombinase and the other plasmid that carries the excision substrate P(glnA)-attL-T1/T2-attR-lacZ, where T1/T2 are the strong transcription terminators of rrnB, to prevent expression of the lacZ reporter under the constitutive promoter P(glnA). The Int-catalyzed site-specific recombination reaction was monitored by the expression of lacZ emanating as a result of T1/T2 excision. Int catalyzed the site-specific excision reaction in Anabaena cells when its substrate was located either on the plasmid or on the chromosome with no need to supply an accessory protein, such as integration host factor and excisionase (Xis), which are indispensable for this reaction in its host, E. coli.

The first characterization of free radicals formed from cellular COX-catalyzed peroxidation.

PubMed

Gu, Yan; Xu, Yi; Law, Benedict; Qian, Steven Y

2013-04-01

Through free radical-mediated peroxidation, cyclooxygenase (COX) can metabolize dihomo-γ-linolenic acid (DGLA) and arachidonic acid (AA) to form well-known bioactive metabolites, namely, the 1-series of prostaglandins (PGs1) and the 2-series of prostaglandins (PGs2), respectively. Unlike PGs2, which are generally viewed as proinflammatory and procarcinogenic PGs, PGs1 may possess anti-inflammatory and anti-cancer activity. Previous studies using ovine COX along with spin trapping and the LC/ESR/MS technique have shown that certain exclusive free radicals are generated from different free radical reactions in DGLA and AA peroxidation. However, it has been unclear whether the differences were associated with the contrasting bioactivity of DGLA vs AA. The aim of this study was to refine the LC/MS and spin trapping technique to make it possible for the association between free radicals and cancer cell growth to be directly tested. Using a colon cancer cell line, HCA-7 colony 29, and LC/MS along with a solid-phase extraction, we were able to characterize the reduced forms of radical adducts (hydroxylamines) as the free radicals generated from cellular COX-catalyzed peroxidation. For the first time, free radicals formed in the COX-catalyzed peroxidation of AA vs DGLA and their association with cancer cell growth were assessed (cell proliferation via MTS and cell cycle distribution via propidium iodide staining) in the same experimental setting. The exclusive free radicals formed from the COX-catalyzed peroxidation of AA and DGLA were shown to be correlated with the cell growth response. Our results indicate that free radicals generated from the distinct radical reactions in COX-catalyzed peroxidation may represent the novel metabolites of AA and DGLA that correspond to their contrasting bioactivity. Copyright © 2012 Elsevier Inc. All rights reserved.

The First Characterization of Free Radicals Formed From Cellular COX-Catalyzed Peroxidation

PubMed Central

Gu, Yan; Xu, Yi; Law, Benedict; Qian, Steven Y.

2014-01-01

Through free radical-mediated peroxidation, cyclooxygenase (COX) can metabolize dihomo-γ-linolenic acid (DGLA) and arachidonic acid(AA) to form well-known bioactive metabolites, namely, the 1-series of prostaglandins (PGs1) and 2-series of prostaglandins(PGs2), respectively. Unlike PGs2, which are generally viewed as pro-inflammatory and pro-carcinogenic PGs, PGs1 may possess anti-inflammatory and anti-cancer activity. Previous studies using ovine COX along with spin trapping and the LC/ESR/MS technique have shown that certain exclusive free radicals are generated from different free radical reactions in DGLA and AA peroxidation. However, it has been unclear whether the differences were associated with the contrasting bioactivity of DGLA vs. AA. The aim of this study was to refine the LC/MS and spin-trapping technique to make it possible for the association between free radicals and cancer cell growth to be directly tested. Using a colon cancer cell line, HCA-7 colony 29, and LC/MS along with a solid phase extraction, we were able to characterize the reduced forms of radical adducts (hydroxylamines) as the free radicals generated from cellular COX-catalyzed peroxidation. For the first time, free radicals formed in the COX-catalyzed peroxidation of AA vs. DGLA and their association with cancer cell growth was assessed (cell proliferation via MTS and cell cycle distribution via PI staining) in the same experimental setting. The exclusive free radicals formed from the COX-catalyzed peroxidation of AA and DGLA were shown to be correlated with the cell growth response. Our results indicate that free radicals generated from the distinct radical reactions in COX-catalyzed peroxidation may represent the novel metabolites of AA and DGLA that correspond to their contrasting bioactivity. PMID:23261941

Regioselective palladium-catalyzed ring-opening reactions of C1-substituted oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylates

PubMed Central

Edmunds, Michael; Raheem, Mohammed Abdul; Boutin, Rebecca; Tait, Katrina

2016-01-01

Summary Palladium-catalyzed ring-opening reactions of C1 substituted 7-oxanorbornadiene derivatives with aryl iodides were investigated. The optimal conditions for this reaction were found to be PdCl2(PPh3)2, ZnCl2, Et3N and Zn in THF. Both steric and electronic factors played a role in the outcome of the reaction as increasing the steric bulk on the bridgehead carbon decreased the yield. These reactions were found to be highly regioselective, giving only one of the two possible regioisomers in all cases. A diverse collection of novel, highly substituted biphenyl derivatives were obtained. PMID:26977182

Endoxifen and Other Metabolites of Tamoxifen Inhibit Human Hydroxysteroid Sulfotransferase 2A1 (hSULT2A1)

PubMed Central

Squirewell, Edwin J.; Qin, Xiaoyan

2014-01-01

Although tamoxifen is a successful agent for treatment and prevention of estrogen-dependent breast cancer, its use has been limited by the low incidence of endometrial cancer. Human hydroxysteroid sulfotransferase 2A1 (hSULT2A1) catalyzes the formation of an α-sulfooxy metabolite of tamoxifen that is reactive toward DNA, and this has been implicated in its carcinogenicity. Also, hSULT2A1 functions in the metabolism of steroid hormones such as dehydroepiandrosterone (DHEA) and pregnenolone (PREG). These roles of hSULT2A1 in steroid hormone metabolism and in generating a reactive metabolite of tamoxifen led us to examine its interactions with tamoxifen and several of its major metabolites. We hypothesized that metabolites of tamoxifen may regulate the catalytic activity of hSULT2A1, either through direct inhibition or through serving as alternate substrates for the enzyme. We found that 4-hydroxy-N-desmethyltamoxifen (endoxifen) is a potent inhibitor of hSULT2A1-catalyzed sulfation of PREG and DHEA, with Ki values of 3.5 and 2.8 μM, respectively. In the hSULT2A1-catalyzed sulfation of PREG, 4-hydroxytamoxifen (4-OHTAM) and N-desmethyltamoxifen (N-desTAM) exhibited Ki values of 12.7 and 9.8 μM, respectively, whereas corresponding Ki values of 19.4 and 17.2 μM were observed with DHEA as substrate. A Ki value of 9.1 μM was observed for tamoxifen-N-oxide with DHEA as substrate, and this increased to 16.9 μM for the hSULT2A1-catalyzed sulfation of PREG. Three metabolites were substrates for hSULT2A1, with relative sulfation rates of 4-OHTAM > N-desTAM > > endoxifen. These results may be useful in interpreting ongoing clinical trials of endoxifen and in improving the design of related molecules. PMID:25157097

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

PubMed Central

Metaxas, Ioannis; Vasilikogiannaki, Eleni

2017-01-01

A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity. PMID:29231853

New synthesis of artepillin C, a prenylated phenol, utilizing lipase-catalyzed regioselective deacetylation as the key step.

PubMed

Yashiro, Kazuki; Hanaya, Kengo; Shoji, Mitsuru; Sugai, Takeshi

2015-01-01

We have synthesized artepillin C, a diprenylated p-hydroxycinnamate originally isolated from Brazilian propolis and exhibiting antioxidant and antitumor activities, from 2,6-diallylphenol. Replacement of the terminal vinyl with 2,2-dimethylvinyl group by olefin cross-metathesis and subsequent transformation yielded 2,6-diprenyl-1,4-hydroquinone diacetate. Candida antarctica lipase B-catalyzed deacetylation in 2-propanol regioselectively removed the less hindered acetyl group to give 2,6-diprenyl-1,4-hydroquinone 1-monoacetate. After triflation of the liberated 4-hydroxy group, a three-carbon side chain was introduced by palladium-mediated alkenylation with methyl acrylate. Final hydrolysis of the esters furnished artepillin C.

Biochemical identification of residues that discriminate between 3,4-dihydroxyphenylalanine decarboxylase and 3,4-dihydroxyphenylacetaldehyde synthase-mediated reactions.

PubMed

Liang, Jing; Han, Qian; Ding, Haizhen; Li, Jianyong

2017-12-01

In available insect genomes, there are several L-3,4-dihydroxyphenylalanine (L-dopa) decarboxylase (DDC)-like or aromatic amino acid decarboxylase (AAAD) sequences. This contrasts to those of mammals whose genomes contain only one DDC. Our previous experiments established that two DDC-like proteins from Drosophila actually mediate a complicated decarboxylation-oxidative deamination process of dopa in the presence of oxygen, leading to the formation of 3,4-dihydroxyphenylacetaldehyde (DHPA), CO 2 , NH 3, and H 2 O 2 . This contrasts to the typical DDC-catalyzed reaction, which produces CO 2 and dopamine. These DDC-like proteins were arbitrarily named DHPA synthases based on their critical role in insect soft cuticle formation. Establishment of reactions catalyzed by these AAAD-like proteins solved a puzzle that perplexed researchers for years, but to tell a true DHPA synthase from a DDC in the insect AAAD family remains problematic due to high sequence similarity. In this study, we performed extensive structural and biochemical comparisons between DHPA synthase and DDC. These comparisons identified several target residues potentially dictating DDC-catalyzed and DHPA synthase-catalyzed reactions, respectively. Comparison of DHPA synthase homology models with crystal structures of typical DDC proteins, particularly residues in the active sites, provided further insights for the roles these identified target residues play. Subsequent site-directed mutagenesis of the tentative target residues and activity evaluations of their corresponding mutants determined that active site His192 and Asn192 are essential signature residues for DDC- and DHPA synthase-catalyzed reactions, respectively. Oxygen is required in DHPA synthase-mediated process and this oxidizing agent is reduced to H 2 O 2 in the process. Biochemical assessment established that H 2 O 2 , formed in DHPA synthase-mediated process, can be reused as oxidizing agent and this active oxygen species is reduced to H 2 O; thereby avoiding oxidative stress by H 2 O 2 . Results of our structural and functional analyses provide a reasonable explanation of mechanisms involved in DHPA synthase-mediated reactions. Based on the key active site residue Asn192, identified in Drosophila DHPA synthase, we were able to distinguish all available insect DHPA synthases from DDC sequences primarily. Copyright © 2017. Published by Elsevier Ltd.

Heteropoly acid-catalyzed microwave-assisted three-component aza-Diels-Alder cyclizations: diastereoselective synthesis of potential drug candidates for Alzheimer's disease.

PubMed

Borkin, Dmitry; Morzhina, Elena; Datta, Silpi; Rudnitskaya, Aleksandra; Sood, Abha; Török, Marianna; Török, Béla

2011-03-07

A highly diastereoselective microwave-assisted three component synthesis of azabicyclo[2.2.2]octan-5-ones by a silicotungstic acid-catalyzed aza-Diels-Alder cyclization is described. The one-pot process involves the formation of the in situ generated Schiff base and its immediate cyclization with cyclohex-2-enone. The short reaction times, good yields and excellent diastereoselectivity make this annulation a practical and environmentally attractive method for the synthesis of the target compounds. Preliminary assays were carried out to determine the activity of the products in AChE as well as in amyloid β fibrillogenesis inhibition.

Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.

Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO 2-supported gold nanoparticles (Au/CeO 2) and Aerosil 200 in the presence of an atmosphere of O 2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species,more » 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO 2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.« less

Aerobic oxidation of cyclic amines to lactams catalyzed by ceria-supported nanogold

DOE PAGES

Dairo, Taiwo O.; Nelson, Nicholas C.; Slowing, Igor I.; ...

2016-09-23

Here, the oxidative transformation of cyclic amines to lactams, which are important chemical feedstocks, is efficiently catalyzed by CeO 2-supported gold nanoparticles (Au/CeO 2) and Aerosil 200 in the presence of an atmosphere of O 2. The complete conversion of pyrrolidine was achieved in 6.5 h at 160 °C, affording a 97 % yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83 % yield) in 2.5 h. Caprolactam, the precursor to the commercially important nylon-6, was obtained from hexamethyleneimine in 37 % yield in 3 h. During the oxidation of pyrrolidine, two transient species,more » 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one, were observed. Both of these compounds were oxidized to 2-pyrrolidone under catalytic conditions, indicating their role as intermediates in the reaction pathway. In addition to the reactions of cyclic secondary amines, Au/CeO 2 also efficiently catalyzes the oxidation of N-methyl cyclic tertiary amines to the corresponding lactams at 80 and 100 °C.« less

Glycal Formation in Crystals of Uridine Phosphorylase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paul, Debamita; O’Leary, Sen E.; Rajashankar, Kanagalaghatta

2010-06-22

Uridine phosphorylase is a key enzyme in the pyrimidine salvage pathway. This enzyme catalyzes the reversible phosphorolysis of uridine to uracil and ribose 1-phosphate (or 2{prime}-deoxyuridine to 2{prime}-deoxyribose 1-phosphate). Here we report the structure of hexameric Escherichia coli uridine phosphorylase treated with 5-fluorouridine and sulfate and dimeric bovine uridine phosphorylase treated with 5-fluoro-2{prime}-deoxyuridine or uridine, plus sulfate. In each case the electron density shows three separate species corresponding to the pyrimidine base, sulfate, and a ribosyl species, which can be modeled as a glycal. In the structures of the glycal complexes, the fluorouracil O2 atom is appropriately positioned to actmore » as the base required for glycal formation via deprotonation at C2{prime}. Crystals of bovine uridine phosphorylase treated with 2{prime}-deoxyuridine and sulfate show intact nucleoside. NMR time course studies demonstrate that uridine phosphorylase can catalyze the hydrolysis of the fluorinated nucleosides in the absence of phosphate or sulfate, without the release of intermediates or enzyme inactivation. These results add a previously unencountered mechanistic motif to the body of information on glycal formation by enzymes catalyzing the cleavage of glycosyl bonds.« less

Rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes through C(sp²)-H/alkene functionalization.

PubMed

Zhou, Ming-Bo; Pi, Rui; Hu, Ming; Yang, Yuan; Song, Ren-Jie; Xia, Yuanzhi; Li, Jin-Heng

2014-10-13

This study describes a new rhodium(III)-catalyzed [3+2] annulation of 5-aryl-2,3-dihydro-1H-pyrroles with internal alkynes using a Cu(OAc)2 oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp(2))-H bond and addition/protonolysis of an alkene C=C bond. This method is applicable to a wide range of 5-aryl-2,3-dihydro-1H-pyrroles and internal alkynes, and results in the assembly of the spiro[indene-1,2'-pyrrolidine] architectures in good yields with excellent regioselectivities. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel-based Enzyme Systems*

PubMed Central

Ragsdale, Stephen W.

2009-01-01

Of the eight known nickel enzymes, all but glyoxylase I catalyze the use and/or production of gases central to the global carbon, nitrogen, and oxygen cycles. Nickel appears to have been selected for its plasticity in coordination and redox chemistry and is able to cycle through three redox states (1+, 2+, 3+) and to catalyze reactions spanning ∼1.5 V. This minireview focuses on the catalytic mechanisms of nickel enzymes, with an emphasis on the role(s) of the metal center. The metal centers vary from mononuclear to complex metal clusters and catalyze simple hydrolytic to multistep redox reactions. PMID:19363030

A beta-keto ester as a novel, efficient, and versatile ligand for copper(I)-catalyzed C-N, C-O, and C-S coupling reactions.

PubMed

Lv, Xin; Bao, Weiliang

2007-05-11

Employing ethyl 2-oxocyclohexanecarboxylate as a novel, efficient, and versatile ligand, the copper-catalyzed coupling reactions of various N/O/S nucleophilic reagents with aryl halides could be successfully carried out under mild conditions. A variety of products including N-arylamides, N-arylimidazoles, aryl ethers, and aryl thioethers were synthesized in good to excellent yields.

Palladium-Catalyzed, Copper(I)-Mediated Coupling of Boronic Acids and Benzylthiocyanate. A Cyanide-Free Cyanation of Boronic Acids

PubMed Central

Zhang, Zhihui; Liebeskind, Lanny S.

2008-01-01

A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields. PMID:16956219

A combined mechanistic and computational study of the gold(I)-catalyzed formation of substituted indenes.

PubMed

Nun, Pierrick; Gaillard, Sylvain; Poater, Albert; Cavallo, Luigi; Nolan, Steven P

2011-01-07

Substituted indenes can be prepared after a sequence [1,3] O-acyl shift-hydroarylation-[1,3] O-acyl shift. Each step is catalyzed by a cationic NHC-Gold(I) species generated in situ after reaction between [(IPr)AuOH] and HBF(4)·OEt(2). This interesting silver-free way is fully supported by a computational study justifying the formation of each intermediate.

Characterization and analysis of the molecular weight of lignin for biorefining studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolbert, Allison; Akinosho, Hannah; Khunsupat, Ratayakorn

2014-06-04

The molecular weight of lignin is a fundamental property that infl uences the recalcitrance of biomass and the valorization of lignin. The determination of the molecular weight of lignin in native biomass is dependent on the bioresources used and the isolation and purifi cation procedures employed. The three most commonly employed isolation methods are milled wood lignin (MWL), cellulolytic enzyme lignin (CEL), and enzymatic mild acidolysis lignin (EMAL). Common characterization techniques for determining the molecular weight of lignin will be addressed, with an emphasis on gel permeation chromatography (GPC). This review also examines the mechanisms behind several biological, physical, andmore » chemical pre-treatments and their impact on the molecular weight of lignin. The number average molecular weight (Mn), weight average molecular weight (Mw) and polydispersity index (D) all vary in magnitude depending on the biomass source, pre-treatment conditions, and isolation method. Additionally, there is a growing body of literature that supports changes in the molecular weight of lignin in response to genetic modifi cations in the lignin biosynthetic pathways. This review summarizes different procedures for obtaining the molecular weight of lignin that have been used in recent years and highlight future opportunities for applications of lignin.« less

6-Azabicyclo[3.2.1]octanes Via Copper-Catalyzed Enantioselective Alkene Carboamination

PubMed Central

Casavant, Barbara J.; Hosseini, Azade S.

2014-01-01

Bridged bicyclic rings containing nitrogen heterocycles are important motifs in bioactive small organic molecules. An enantioselective copper-catalyzed alkene carboamination reaction that creates bridged heterocycles is reported herein. Two new rings are formed in this alkene carboamination reaction where N-sulfonyl-2-aryl-4-pentenamines are converted to 6-azabicyclo[3.2.1]octanes using [Ph-Box-Cu](OTf)2 or related catalysts in the presence of MnO2 as stoichiometric oxidant in moderate to good yields and generally excellent enantioselectivities. Two new stereocenters are formed in the reaction, and the C-C bond-forming arene addition is a net C-H functionalization. PMID:25484848

Computational Studies on the Pt(II)-Catalyzed Cycloisomerization of 1,6-dienes into Bicyclopropanes: A Mechanistic Quandary Evaluated by DFT

PubMed Central

Bell, Franziska; Holland, Jason; Green, Jennifer C.; Gagné, Michel R.

2009-01-01

The mechanism of the (bis(phosphanylethyl)phosphane)Pt2+ catalyzed cyclo-isomerization reaction of 7-methyl-octa-1,6-diene to form 1-isopropylbicyclo[3.1.0]hexane was studied using computational methods. The cyclopropanation step was found to be the turnover-limiting step. The overall reaction proceeds via both a 5-exo and a 6-endo route. W conformations were shown to facilitate cyclopropanation, but do not have any influence on the rate of the 1,2-hydride shifts. PMID:20161262

Acid-catalyzed autohydrolysis of wheat straw to improve sugar recovery.

PubMed

Ertas, Murat; Han, Qiang; Jameel, Hasan

2014-10-01

A comparison study of autohydrolysis and acid-catalyzed autohydrolysis of wheat straw was performed to understand the impact of acid addition on overall sugar recovery. Autohydrolysis combined with refining is capable of achieving sugar recoveries in the mid 70s. If the addition of a small amount of acid is capable of increasing the sugar recovery even higher it may be economically attractive. Acetic, sulfuric, hydrochloric and sulfurous acids were selected for acid-catalyzed autohydrolysis pretreatments. Autohydrolysis with no acid at 190 °C showed the highest total sugar in the prehydrolyzate. Enzymatic hydrolysis was performed for all the post-treated solids with and without refining at enzyme loadings of 4 and 10 FPU/g for 96 h. Acid-catalyzed autohydrolysis at 190 °C with sulfurous acid showed the highest total sugar recovery of 81.2% at 4 FPU/g enzyme charge compared with 64.3% at 190 °C autohydrolysis without acid. Copyright © 2014 Elsevier Ltd. All rights reserved.

Human reductive halothane metabolism in vitro is catalyzed by cytochrome P450 2A6 and 3A4.

PubMed

Spracklin, D K; Thummel, K E; Kharasch, E D

1996-09-01

The anesthetic halothane undergoes extensive oxidative and reductive biotransformation, resulting in metabolites that cause hepatotoxicity. Halothane is reduced anaerobically by cytochrome P450 (P450) to the volatile metabolites 2-chloro-1,1-difluoroethene (CDE) and 2-chloro-1,1,1-trifluoroethane (CTE). The purpose of this investigation was to identify the human P450 isoform(s) responsible for reductive halothane metabolism. CDE and CTE formation from halothane metabolism by human liver microsomes was determined by GC/MS analysis. Halothane metabolism to CDE and CTE under reductive conditions was completely inhibited by carbon monoxide, which implicates exclusively P450 in this reaction. Eadie-Hofstee plots of both CDE and CTE formation were nonlinear, suggesting multiple P450 isoform involvement. Microsomal CDE and CTE formation were each inhibited 40-50% by P450 2A6-selective inhibitors (coumarin and 8-methoxypsoralen) and 55-60% by P450 3A4-selective inhibitors (ketoconazole and troleandomycin). P450 1A-, 2B6-, 2C9/10-, and 2D6-selective inhibitors (7,8-benzoflavone, furafylline, orphenadrine, sulfaphenazole, and quinidine) had no significant effect on reductive halothane metabolism. Measurement of product formation catalyzed by a panel of cDNA-expressed P450 isoforms revealed that maximal rates of CDE formation occurred with P450 2A6, followed by P450 3A4. P450 3A4 was the most effective catalyst of CTE formation. Among a panel of 11 different human livers, there were significant linear correlations between the rate of CDE formation and both 2A6 activity (r = 0.64, p < 0.04) and 3A4 activity (r = 0.64, p < 0.03). Similarly, there were significant linear correlations between CTE formation and both 2A6 activity (r = 0.55, p < 0.08) and 3A4 activity (r = 0.77, p < 0.005). The P450 2E1 inhibitors 4-methylpyrazole and diethyldithiocarbamate inhibited CDE and CTE formation by 20-45% and 40-50%, respectively; however, cDNA-expressed P450 2E1 did not catalyze significant amounts of CDE or CTE production, and microsomal metabolite formation was not correlated with P450 2E1 activity. This investigation demonstrated that human liver microsomal reductive halothane metabolism is catalyzed predominantly by P450 2A6 and 3A4. This isoform selectivity for anaerobic halothane metabolism contrasts with that for oxidative human halothane metabolism, which is catalyzed predominantly by P450 2E1.

Herb–drug interaction prediction based on the high specific inhibition of andrographolide derivatives towards UDP-glucuronosyltransferase (UGT) 2B7

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Hai-Ying, E-mail: cmu4h-mhy@126.com; Sun, Dong-Xue; Cao, Yun-Feng

2014-05-15

Herb–drug interaction strongly limits the clinical application of herbs and drugs, and the inhibition of herbal components towards important drug-metabolizing enzymes (DMEs) has been regarded as one of the most important reasons. The present study aims to investigate the inhibition potential of andrographolide derivatives towards one of the most important phase II DMEs UDP-glucuronosyltransferases (UGTs). Recombinant UGT isoforms (except UGT1A4)-catalyzed 4-methylumbelliferone (4-MU) glucuronidation reaction and UGT1A4-catalyzed trifluoperazine (TFP) glucuronidation were employed to firstly screen the andrographolide derivatives' inhibition potential. High specific inhibition of andrographolide derivatives towards UGT2B7 was observed. The inhibition type and parameters (K{sub i}) were determined for themore » compounds exhibiting strong inhibition capability towards UGT2B7, and human liver microsome (HLMs)-catalyzed zidovudine (AZT) glucuronidation probe reaction was used to furtherly confirm the inhibition behavior. In combination of inhibition parameters (K{sub i}) and in vivo concentration of andrographolide and dehydroandrographolide, the potential in vivo inhibition magnitude was predicted. Additionally, both the in vitro inhibition data and computational modeling results provide important information for the modification of andrographolide derivatives as selective inhibitors of UGT2B7. Taken together, data obtained from the present study indicated the potential herb–drug interaction between Andrographis paniculata and the drugs mainly undergoing UGT2B7-catalyzed metabolic elimination, and the andrographolide derivatives as potential candidates for the selective inhibitors of UGT2B7. - Highlights: • Specific inhibition of andrographolide derivatives towards UGT2B7. • Herb-drug interaction related withAndrographis paniculata. • Guidance for design of UGT2B7 specific inhibitors.« less

Glutaredoxin GrxC2 catalyzes the glutathionylation and inactivation of Arabidopsis BRI1-ASSOCIATED RECEPTOR-LIKE KINASE 1 (BAK1) in vitro

USDA-ARS?s Scientific Manuscript database

Reversible protein phosphorylation, catalyzed by protein kinases, is the most widely studied post-translational modification (PTM) both in terms of its occurrence and the regulatory consequences of phosphorylation events on phosphorylated proteins. In addition to reversible phosphorylation, many pro...

N-heterocyclic carbene catalyzed regioselective oxo-acyloxylation of alkenes with aromatic aldehydes: a high yield synthesis of α-acyloxy ketones and esters.

PubMed

Reddi, Rambabu N; Malekar, Pushpa V; Sudalai, Arumugam

2013-10-14

An N-heterocyclic carbene (NHC)-catalyzed reaction of alkenes with aromatic aldehydes providing for a high yield synthesis of α-acyloxy ketones and esters has been described. This unprecedented regioselective oxidative process employs NBS and Et3N in stoichiometric amounts and O2 (1 atm) as an oxidant under ambient conditions in DMSO as a solvent.

Ferrocene-catalyzed heterogeneous Fenton-like degradation mechanisms and pathways of antibiotics under simulated sunlight: A case study of sulfamethoxazole.

PubMed

Li, Yingjie; Zhang, Biaojun; Liu, Xiangliang; Zhao, Qun; Zhang, Heming; Zhang, Yuechao; Ning, Ping; Tian, Senlin

2018-07-05

Readily-available and efficient catalyst is essential for activating oxidants to produce reactive species for deeply remediating water bodies contaminated by antibiotics. In this study, Ferrocene (Fc) was introduced to establish a heterogeneous photo-Fenton system for the degradation of sulfonamide antibiotics, taking sulfamethoxazole as a representative. Results showed that the removal of sulfamethoxazole was effective in Fc-catalyzed photo-Fenton system. Electron spin resonance and radical scavenging experiments verified that there was a photoindued electron transfer process from Fc to H 2 O 2 and dissolved oxygen resulting in the formation of OH that was primarily responsible for the degradation of sulfamethoxazole. The reactions of OH with substructure model compounds of sulfamethoxazole unveiled that aniline moiety was the preferable reaction site of sulfamethoxazole, which was verified by the formation of hydroxylated product and the dimer of sulfamethoxazole in Fc-catalyzed photo-Fenton system. This heterogeneous photo-Fenton system displayed an effective degradation efficiency even in a complex water matrices, and Fc represented a long-term stability by using the catalyst for multiple cycles. These results demonstrate that Fc-catalyzed photo-Fenton oxidation may be an efficient approach for remediation of wastewater containing antibiotics. Copyright © 2018. Published by Elsevier B.V.

Divergent Syntheses of Isoquinolines and Indolo[1,2-a]quinazolines by Copper-Catalyzed Cascade Annulation from 2-Haloaryloxime Acetates with Active Methylene Compounds and Indoles.

PubMed

Jiang, Huanfeng; Yang, Jidan; Tang, Xiaodong; Wu, Wanqing

2016-03-04

A convenient and reliable method for the direct construction of isoquinolines is described. A series of isoquinoline derivatives were synthesized, with high chemo- and regioselectivities, via the copper-catalyzed cascade reaction of 2-haloaryloxime acetates with β-diketones, β-keto esters, and β-keto nitriles. This tandem annulation process features inexpensive catalysts, no need for additional ligands, and excellent functional group tolerance, which makes it have potential synthetic applications. Furthermore, this strategy could also be used to enter functionalized indolo[1,2-a]quinazolines by using indoles as the counterpart of the 2-haloaryloxime acetates.

Substrate-controlled Rh(II)-catalyzed single-electron-transfer (SET): divergent synthesis of fused indoles.

PubMed

Chen, Kai; Zhu, Zi-Zhong; Liu, Jia-Xin; Tang, Xiang-Ying; Wei, Yin; Shi, Min

2016-01-07

Rh(II)-catalyzed diversified ring expansions controlled by single-electron-transfer (SET) have been disclosed in this communication, producing a series of indole-fused azetidines and 1H-carbazoles or related derivatives in moderate to good yields via Rh2(III,II) nitrene radical intermediates. The direction of ring expansion branches according to different ring sizes of methylenecycloalkanes.

Lysophosphatidylcholine synthesis by lipase-catalyzed ethanolysis.

PubMed

Yang, Guolong; Yang, Ruoxi; Hu, Jingbo

2015-01-01

Lysophosphatidylcholine (LPC) is amphiphilic substance, and possesses excellent physiological functions. In this study, LPC was prepared through ethanolysis of phosphatidylcholine (PC) in n-hexane or solvent free media catalyzed by Novozym 435 (from Candida antarctica), Lipozyme TLIM (from Thermomcyces lanuginosus) and Lipozyme RMIM (from Rhizomucor miehei). The results showed that three immobilized lipases from Candida Antarctica, Thermomcyces lanuginosus and Rhizomucor miehei could catalyze ethanolysis of PC efficiently. In n-hexane, the LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TLIM and Lipozyme RMIM could reach to 98.5 ± 1.6%, 94.6 ± 1.4% and 93.7 ± 1.8%, respectively. In solvent free media, the highest LPC conversions of ethanolysis of PC catalyzed by Novozyme 435, Lipozyme TL IM and Lipozyme RM IM were 97.7 ± 1.7%, 93.5 ± 1.2% and 93.8 ± 1.9%, respectively. The catalytic efficiencies of the three lipases were in the order of Novozyme 435 > Lipozyme TLIM > Lipozyme RMIM. Furthermore, their catalytic efficiencies in n-hexane were better than those in solvent free media.

Isotope Effects Reveal the Mechanism of Enamine Formation in l-Proline-Catalyzed α-Amination of Aldehydes.

PubMed

Ashley, Melissa A; Hirschi, Jennifer S; Izzo, Joseph A; Vetticatt, Mathew J

2016-02-17

The mechanism of l-proline-catalyzed α-amination of 3-phenylpropionaldehyde was studied using a combination of experimental kinetic isotope effects (KIEs) and theoretical calculations. Observation of a significant carbonyl (13)C KIE and a large primary α-deuterium KIE support rate-determining enamine formation. Theoretical predictions of KIEs exclude the widely accepted mechanism of enamine formation via intramolecular deprotonation of an iminium carboxylate intermediate. An E2 elimination mechanism catalyzed by a bifunctional base that directly forms an N-protonated enamine species from an oxazolidinone intermediate accounts for the experimental KIEs. These findings provide the first experimental picture of the transition-state geometry of enamine formation and clarify the role of oxazolidinones as nonparasitic intermediates in proline catalysis.

Preparative and mechanistic studies toward the rational development of catalytic, enantioselective selenoetherification reactions.

PubMed

Denmark, Scott E; Kalyani, Dipannita; Collins, William R

2010-11-10

A systematic investigation into the Lewis base catalyzed, asymmetric, intramolecular selenoetherification of olefins is described. A critical challenge for the development of this process was the identification and suppression of racemization pathways available to arylseleniranium ion intermediates. This report details a thorough study of the influences of the steric and electronic modulation of the arylselenenyl group on the configurational stability of enantioenriched seleniranium ions. These studies show that the 2-nitrophenyl group attached to the selenium atom significantly attenuates the racemization of seleniranium ions. A variety of achiral Lewis bases catalyze the intramolecular selenoetherification of alkenes using N-(2-nitrophenylselenenyl)succinimide as the electrophile along with a Brønsted acid. Preliminary mechanistic studies suggest the intermediacy of ionic Lewis base-selenium(II) adducts. Most importantly, a broad survey of chiral Lewis bases revealed that 1,1'-binaphthalene-2,2'-diamine (BINAM)-derived thiophosphoramides catalyze the cyclization of unsaturated alcohols in the presence of N-(2-nitrophenylselenenyl)succinimide and methanesulfonic acid. A variety of cyclic seleno ethers were produced in good chemical yields and in moderate to good enantioselectivities, which constitutes the first catalytic, enantioselective selenofunctionalization of unactivated olefins.

The Tautomeric Half-reaction of BphD, a C-C Bond Hydrolase Kinetic and Structural Evidence Supporting a Key Role for Histidine 265 of the Catalytic triad

DOE Office of Scientific and Technical Information (OSTI.GOV)

Horsman, Geoff P.; Bhowmik, Shiva; Seah, Stephen Y.K.

2010-01-07

BphD of Burkholderia xenovorans LB400 catalyzes an unusual C-C bond hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid (HOPDA) to afford benzoic acid and 2-hydroxy-2,4-pentadienoic acid (HPD). An enol-keto tautomerization has been proposed to precede hydrolysis via a gem-diol intermediate. The role of the canonical catalytic triad (Ser-112, His-265, Asp-237) in mediating these two half-reactions remains unclear. We previously reported that the BphD-catalyzed hydrolysis of HOPDA ({lambda}{sub max} is 434 nm for the free enolate) proceeds via an unidentified intermediate with a red-shifted absorption spectrum ({lambda}{sub max} is 492 nm) (Horsman, G. P., Ke, J., Dai, S., Seah, S. Y. K., Bolin, J. T.,more » and Eltis, L. D. (2006) Biochemistry 45, 11071-11086). Here we demonstrate that the S112A variant generates and traps a similar intermediate ({lambda}{sub max} is 506 nm) with a similar rate, 1/{tau} {approx} 500 s{sup -1}. The crystal structure of the S112A:HOPDA complex at 1.8-{angstrom} resolution identified this intermediate as the keto tautomer, (E)-2,6-dioxo-6-phenyl-hex-3-enoate. This keto tautomer did not accumulate in either the H265A or the S112A/H265A double variants, indicating that His-265 catalyzes tautomerization. Consistent with this role, the wild type and S112A enzymes catalyzed tautomerization of the product HPD, whereas H265A variants did not. This study thus identifies a keto intermediate, and demonstrates that the catalytic triad histidine catalyzes the tautomerization half-reaction, expanding the role of this residue from its purely hydrolytic function in other serine hydrolases. Finally, the S112A:HOPDA crystal structure is more consistent with hydrolysis occurring via an acyl-enzyme intermediate than a gem-diol intermediate as solvent molecules have poor access to C6, and the closest ordered water is 7{angstrom} away.« less

Mechanism of xanthine oxidase catalyzed biotransformation of HMX under anaerobic conditions.

PubMed

Bhushan, Bharat; Paquet, Louise; Halasz, Annamaria; Spain, Jim C; Hawari, Jalal

2003-06-27

Enzyme catalyzed biotransformation of the energetic chemical octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is not known. The present study describes a xanthine oxidase (XO) catalyzed biotransformation of HMX to provide insight into the biodegradation pathway of this energetic chemical. The rates of biotransformation under aerobic and anaerobic conditions were 1.6+/-0.2 and 10.5+/-0.9 nmolh(-1)mgprotein(-1), respectively, indicating that anaerobic conditions favored the reaction. The biotransformation rate was about 6-fold higher using NADH as an electron-donor compared to xanthine. During the course of reaction, the products obtained were nitrite (NO(2)(-)), methylenedinitramine (MDNA), 4-nitro-2,4-diazabutanal (NDAB), formaldehyde (HCHO), nitrous oxide (N(2)O), formic acid (HCOOH), and ammonium (NH(4)(+)). The product distribution gave carbon and nitrogen mass-balances of 91% and 88%, respectively. A comparative study with native-, deflavo-, and desulfo-XO and the site-specific inhibition studies showed that HMX biotransformation occurred at the FAD-site of XO. Nitrite stoichiometry revealed that an initial single N-denitration step was sufficient for the spontaneous decomposition of HMX.

Palladium-catalyzed cyclocoupling of 2-halobiaryls with isocyanides via the cleavage of carbon-hydrogen bonds.

PubMed

Tobisu, Mamoru; Imoto, Shinya; Ito, Sana; Chatani, Naoto

2010-07-16

To demonstrate the utility of isocyanides in catalytic C-H bond functionalization reactions, a palladium-catalyzed cyclocoupling reaction of 2-halobiaryls with isocyanides was developed. The reaction afforded an array of fluorenone imine derivatives via the cleavage of a C-H bond at the 2'-position of 2-halobiaryls. The use of 2,6-disubstituted phenyl isocyanide was crucial for this catalytic cyclocoupling reaction to proceed. The reaction was applicable to heterocyclic and vinylic substrates, allowing the construction of a wide range of ring system. The large kinetic isotope effect observed (k(H)/k(D) = 5.3) indicates that C-H bond activation was the turnover-limiting step in this catalysis.

Mechanism of the Enantioselective Oxidation of Racemic Secondary Alcohols Catalyzed by Chiral Mn(III)–Salen Complexes

PubMed Central

Brown, M. Kevin; Blewett, Megan M.; Colombe, James R.; Corey, E. J.

2010-01-01

The experiments described here clarify the mechanism and origin of the enantioselectivity of the oxidation of racemic secondary alcohols catalyzed by chiral Mn(III)–salen complexes using HOBr, Br2/H2O/KOAc or PhI(OAc)2/H2O/KBr as a stoichiometric oxidant. Key points of the proposed pathway include (1) the formation of a Mn(V)–salen dibromide, (2) its subsequent reaction with the alcohol to give an alkoxy-Mn(V) species, and (3) carbonyl-forming elimination to produce the ketone via a highly organized transition state with intramolecular transfer of hydrogen from carbon to an oxygen of the salen ligand. PMID:20666410

Diastereoselective Carbocyclization of 1,6-Heptadienes Triggered by Rhodium-Catalyzed Activation of an Olefinic C=H Bond**

PubMed Central

Aïssa, Christophe; Ho, Kelvin Y T; Tetlow, Daniel J; Pin-Nó, María

2014-01-01

The use of α,ω-dienes as functionalization reagents for olefinic carbon–hydrogen bonds has been rarely studied. Reported herein is the rhodium(I)-catalyzed rearrangement of prochiral 1,6-heptadienes into [2,2,1]-cycloheptane derivatives with concomitant creation of at least three stereogenic centers and complete diastereocontrol. Deuterium-labeling studies and the isolation of a key intermediate are consistent with a group-directed C=H bond activation, followed by two consecutive migratory insertions, with only the latter step being diastereoselective. PMID:24634225

Copper-Catalyzed, Directing Group-Assisted Fluorination of Arene and Heteroarene C-H Bonds

PubMed Central

Truong, Thanh; Klimovica, Kristine; Daugulis, Olafs

2013-01-01

We have developed a method for direct, copper-catalyzed, auxiliary-assisted fluorination of β-sp2 C-H bonds of benzoic acid derivatives and γ-sp2 C-H bonds of α,α-disubstituted benzylamine derivatives. The reaction employs CuI catalyst, AgF fluoride source, and DMF, pyridine, or DMPU solvent at moderately elevated temperatures. Selective mono- or difluorination can be achieved by simply changing reaction conditions. The method shows excellent functional group tolerance and provides a straightforward way for the preparation of ortho-fluorinated benzoic acids. PMID:23758609

Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

PubMed

Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

2012-11-16

An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

Aminative umpolung of aldehydes to α-amino anion equivalents for Pd-catalyzed allylation: an efficient synthesis of homoallylic amines.

PubMed

Ding, Lei; Chen, Jing; Hu, Yifan; Xu, Juan; Gong, Xing; Xu, Dongfang; Zhao, Baoguo; Li, Hexing

2014-02-07

An attractive strategy for generation of α-amino anions from aldehydes with applications in synthesis of homoallylic amines is described. Aromatic aldehydes can be converted to α-amino anion equivalents via amination with 2,2-diphenylglycine and subsequent decarboxylation. The in situ generated α-imino anions are highly reactive for Pd-catalyzed allylation, forming the corresponding homoallylic amines in high yields with excellent regioselectivity.

Dinitrosyl iron complexes and S-nitrosothiols are two possible forms for stabilization and transport of nitric oxide in biological systems.

PubMed

Vanin, A F

1998-07-01

The physicochemical properties, mechanisms of synthesis and decomposition of dinitrosyl iron complexes (DNICs) with thiol-containing ligands and of S-nitrosothiols (RS-NO), and the potential role of these compounds in storage and transport of NO in biological systems are reviewed. Special attention is given to the phenomenon of mutual transformation of DNIC and RS-NO catalyzed by Fe2+. Each Fe2+ binds two neutral NO molecules in the DNICs, catalyzes their mutual oxidation--reduction with formation of nitrous oxide and nitrosonium ions appearing in the DNICs. These ions S-nitrosate thiol-compounds with RS-NO formation. Fe2+ binds two RS-NO molecules and catalyzes their mutual oxidation--reduction followed by decomposition of the resulting molecules. Mutual conversion of DNICs and RS-NO regulated by iron, thiol, and NO levels is suggested to provide NO transport in cells and tissues.

Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation reactions.

PubMed

Hua, Yuanda; Nguyen, Hiep H; Scaggs, William R; Jeon, Junha

2013-07-05

Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation of homoallyl silyl ethers (1) exploiting either BINAP or 1,6-bis(diphenylphosphino)hexane (dpph) has been developed. This method permits selective access to either trans-oxasilacyclopentanes (trans-2) or oxasilacyclohexanes (3) at will. A substoichiometric amount of norbornene markedly increased both yield and selectivity. A norbornene-mediated hydride shuttle process is discussed.

Ferrier sulfamidoglycosylation of glycals catalyzed by nitrosonium tetrafluoroborate: towards new carbonic anhydrase glycoinhibitors.

PubMed

Ombouma, Joanna; Vullo, Daniela; Supuran, Claudiu T; Winum, Jean-Yves

2014-11-15

Ferrier sulfamidoglycosylation of glycals catalyzed by nitrosonium tetrafluoroborate allowed the preparation of hydroxysulfamide glycosides in good yields with a good α stereoselectivity. A variety of mono-saccharide derivatives was synthesized using this new methodology leading to selective and powerful glycoinhibitors of the tumor associated carbonic anhydrases (CA, EC 4.2.1.1) isoforms CA IX and CA XII. Copyright © 2014 Elsevier Ltd. All rights reserved.

Use of Aryl Chlorides as Electrophiles in Pd-Catalyzed Alkene Difunctionalization Reactions

PubMed Central

Rosen, Brandon R.; Ney, Joshua E.; Wolfe, John P.

2010-01-01

The development of conditions that allow use of inexpensive aryl chlorides as electrophiles in Pd-catalyzed alkene carboamination and carboetherification reactions is described. A catalyst composed of Pd(OAc)2 and S-Phos minimizes N-arylation of the substrate and prevents formation of mixtures of regioisomeric products. A number of heterocycles, including pyrrolidines, isoxazolidines, tetrahydrofurans, and pyrazolidines, are efficiently generated with this method. PMID:20297834

Gold-catalyzed three-component annulation: efficient synthesis of highly functionalized dihydropyrazoles from alkynes, hydrazines, and aldehydes or ketones.

PubMed

Suzuki, Yamato; Naoe, Saori; Oishi, Shinya; Fujii, Nobutaka; Ohno, Hiroaki

2012-01-06

Polysubstituted dihydropyrazoles were directly obtained by a gold-catalyzed three-component annulation. This reaction consists of a Mannich-type coupling of alkynes with N,N'-disubstituted hydrazines and aldehydes/ketones followed by intramolecular hydroamination. Cascade cyclization using 1,2-dialkynylbenzene derivatives as the alkyne component was also performed producing fused tricyclic dihydropyrazoles in good yields. © 2011 American Chemical Society

Octahedral molecular sieve sorbents and catalysts

DOEpatents

Li, Liyu [Richland, WA; King, David L [Richland, WA

2010-04-20

Octahedral molecular sieve sorbents and catalysts are disclosed, including silver hollandite and cryptomelane. These materials can be used, for example, to catalyze the oxidation of CO.sub.x (e.g., CO), NO.sub.x (e.g., NO), hydrocarbons (e.g., C.sub.3H.sub.6) and/or sulfur-containing compounds. The disclosed materials also may be used to catalyze other reactions, such as the reduction of NO.sub.2. In some cases, the disclosed materials are capable of sorbing certain products from the reactions they catalyze. Silver hollandite, in particular, can be used to remove a substantial portion of certain sulfur-containing compounds from a gas or liquid by catalysis and/or sorption. The gas or liquid can be, for example, natural gas or a liquid hydrocarbon.

Photo-catalyzed surface hydrolysis of iridium(iii) ions on semiconductors: a facile method for the preparation of semiconductor/IrOx composite photoanodes toward oxygen evolution reaction.

PubMed

Wu, Qingyong; Xu, Di; Xue, Ning; Liu, Tengyi; Xiang, Min; Diao, Peng

2016-12-21

We previously reported that the hydrolysis of Ir 3+ in homogeneous solution could be triggered by irradiation with light whose energy was larger than a threshold value. In this work, we demonstrated that, by introducing Fe 2 O 3 particles into solution, the incident light energy-restriction for the photo-catalyzed hydrolysis could be broken and the hydrolysis occurred at the Fe 2 O 3 /solution interface. The photo-generated holes on the Fe 2 O 3 surface played a key role in oxidizing Ir(iii) to Ir(iv) species and triggered the deposition of IrO x . We showed that this photo-catalyzed surface hydrolysis is a universal phenomenon that takes place on the surface of many n-type semiconductors such as Fe 2 O 3 , TiO 2 , and Ag 3 PO 4 . As IrO x is an efficient catalyst for oxygen evolution reaction, surface hydrolysis is a general, facile and efficient strategy to prepare semiconductor/IrO x composites, which can be used as anodic materials for photoelectrochemical water splitting.

Enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7.

PubMed

Fang, Zhong-Ze; Wang, Haina; Cao, Yun-Feng; Sun, Dong-Xue; Wang, Li-Xuan; Hong, Mo; Huang, Ting; Chen, Jian-Xing; Zeng, Jia

2015-03-01

UDP-glucuronosyltransferases (UGTs)-catalyzed glucuronidation conjugation reaction plays an important role in the elimination of many important clinical drugs and endogenous substances. The present study aims to investigate the enantioselective inhibition of carprofen towards UGT isoforms. In vitro a recombinant UGT isoforms-catalyzed 4-methylumbelliferone (4-MU) glucuronidation incubation mixture was used to screen the inhibition potential of (R)-carprofen and (S)-carprofen towards multiple UGT isoforms. The results showed that (S)-carprofen exhibited stronger inhibition potential than (R)-carprofen towards UGT2B7. However, no significant difference was observed for the inhibition of (R)-carprofen and (S)-carprofen towards other UGT isoforms. Furthermore, the inhibition kinetic behavior was compared for the inhibition of (S)-carprofen and (R)-carprofen towards UGT2B7. A Lineweaver-Burk plot showed that both (S)-carprofen and (R)-carprofen exhibited competitive inhibition towards UGT2B7-catalyzed 4-MU glucuronidation. The inhibition kinetic parameter (Ki ) was calculated to be 7.0 μM and 31.1 μM for (S)-carprofen and (R)-carprofen, respectively. Based on the standard for drug-drug interaction, the threshold for (S)-carprofen and (R)-carprofen to induce a drug-drug interaction is 0.7 μM and 3.1 μM, respectively. In conclusion, enantioselective inhibition of carprofen towards UDP-glucuronosyltransferase (UGT) 2B7 was demonstrated in the present study. Using the in vitro inhibition kinetic parameter, the concentration threshold of (S)-carprofen and (R)-carprofen to possibly induce the drug-drug interaction was obtained. Therefore, clinical monitoring of the plasma concentration of (S)-carprofen is more important than (R)-carprofen to avoid a possible drug-drug interaction between carprofen and the drugs mainly undergoing UGT2B7-catalyzed metabolism. © 2014 Wiley Periodicals, Inc.

Product deuterium isotope effects for orotidine 5'-monophosphate decarboxylase: effect of changing substrate and enzyme structure on the partitioning of the vinyl carbanion reaction intermediate.

PubMed

Toth, Krisztina; Amyes, Tina L; Wood, Bryant M; Chan, Kui; Gerlt, John A; Richard, John P

2010-05-26

A product deuterium isotope effect (PIE) of 1.0 was determined as the ratio of the yields of [6-(1)H]-uridine 5'-monophosphate (50%) and [6-(2)H]-uridine 5'-monophosphate (50%) from the decarboxylation of orotidine 5'-monophosphate (OMP) in 50/50 (v/v) HOH/DOD catalyzed by orotidine 5'-monophosphate decarboxylase (OMPDC) from Saccharomyces cerevisiae, Methanothermobacter thermautotrophicus, and Escherichia coli. This unitary PIE eliminates a proposed mechanism for enzyme-catalyzed decarboxylation in which proton transfer from Lys-93 to C-6 of OMP provides electrophilic push to the loss of CO(2) in a concerted reaction. We propose that the complete lack of selectivity for the reaction of solvent H and D, which is implied by the value of PIE = 1.0, is enforced by restricted C-N bond rotation of the -CH(2)-NL(3)(+) group of the side chain of Lys-93. A smaller PIE of 0.93 was determined as the ratio of the product yields for OMPDC-catalyzed decarboxylation of 5-fluoroorotidine 5'-monophosphate (5-FOMP) in 50/50 (v/v) HOH/DOD. Mutations on the following important active-site residues of OMPDC from S. cerevisiae have no effect on the PIE on OMPDC-catalyzed decarboxylation of OMP or decarboxylation of 5-FOMP: R235A, Y217A, Q215A, S124A, and S154A/Q215A.

Product Deuterium Isotope Effects for Orotidine 5'-Monophosphate Decarboxylase: Effect of Changing Substrate and Enzyme Structure on the Partitioning of the Vinyl Carbanion Reaction Intermediate

PubMed Central

Toth, Krisztina; Amyes, Tina L.; Wood, Bryant M.; Chan, Kui; Gerlt, John A.

2010-01-01

A product deuterium isotope effect (PIE) of 1.0 was determined as the ratio of the yields of [6-1H]-uridine 5'-monophosphate (50%) and [6-2H]-uridine 5'-monophosphate (50%) from the decarboxylation of orotidine 5'-monophosphate (OMP) in 50/50 (v/v) HOH/DOD catalyzed by orotidine 5'-monophosphate decarboxylase (OMPDC) from S. cerevisiae, M. thermautotrophicus and E. coli. This unitary PIE eliminates a proposed mechanism for enzyme-catalyzed decarboxylation in which proton transfer from Lys-93 to C-6 of OMP provides electrophilic push to the loss of CO2 in a concerted reaction. We propose that the complete lack of selectivity for the reaction of solvent H and D, that is implied by the value of PIE = 1.0, is enforced by restricted C-N bond rotation of the -CH2-NL3+ group of the side-chain of Lys-93. A smaller PIE of 0.93 was determined as the ratio of the product yields for OMPDC-catalyzed decarboxylation of 5-fluoroorotidine 5'-monophosphate (5-FOMP) in 50/50 (v/v) HOH/DOD. The following mutations of important active site residues of OMPDC from S. cerevisiae have no effect on the PIE on OMPDC-catalyzed decarboxylation of OMP or decarboxylation of 5-FOMP: R235A, Y217A, Q215A, S124A and S154A/Q215A. PMID:20441167

Use of Elemental Sulfur or Selenium in a Novel One-Pot Copper-Catalyzed Tandem Cyclization of Functionalized Ynamides Leading to Benzosultams.

PubMed

Siva Reddy, Alla; Kumara Swamy, K C

2015-06-19

A novel and efficient [Cu]-catalyzed one-pot regio- and stereospecific synthesis of benzo[1,4,2]dithiazine 1,1-dioxides and benzo[1,4,2]thiaselenazine 1,1-dioxides by cyclization of functionalized ynamides with elemental sulfur/selenium has been developed. Its generality is elegantly illustrated by extension to benzodithiazepines and benzothiaselenazepines. Involvement of water in the reaction is demonstrated by the incorporation of (2)D at the olefinic site by using D2O in place of water. Selective oxidation at sulfur in benzo[1,4,2]dithiazine 1,1-dioxide by using mCPBA as the oxidizing agent is also described.

Copper-Catalyzed Chan-Lam Cyclopropylation of Phenols and Azaheterocycles.

PubMed

Derosa, Joseph; O'Duill, Miriam L; Holcomb, Matthew; Boulous, Mark N; Patman, Ryan L; Wang, Fen; Tran-Dubé, Michelle; McAlpine, Indrawan; Engle, Keary M

2018-04-06

Small molecules containing cyclopropane-heteroatom linkages are commonly needed in medicinal chemistry campaigns yet are problematic to prepare using existing methods. To address this issue, a scalable Chan-Lam cyclopropylation reaction using potassium cyclopropyl trifluoroborate has been developed. With phenol nucleophiles, the reaction effects O-cyclopropylation, whereas with 2-pyridones, 2-hydroxybenzimidazoles, and 2-aminopyridines the reaction brings about N-cyclopropylation. The transformation is catalyzed by Cu(OAc) 2 and 1,10-phenanthroline and employs 1 atm of O 2 as the terminal oxidant. This method is operationally convenient to perform and provides a simple, strategic disconnection toward the synthesis of cyclopropyl aryl ethers and cyclopropyl amine derivatives bearing an array of functional groups.

A Price To Pay for Relaxed Substrate Specificity: A Comparative Kinetic Analysis of the Class II Lanthipeptide Synthetases ProcM and HalM2

PubMed Central

2015-01-01

Lanthipeptides are a class of ribosomally synthesized and posttranslationally modified peptide natural products (RiPPs) that typically harbor multiple intramolecular thioether linkages. For class II lanthipeptides, these cross-links are installed in a multistep reaction pathway by a single enzyme (LanM). The multifunctional nature of LanMs and the manipulability of their genetically encoded peptide substrates (LanAs) make LanM/LanA systems promising targets for the engineering of new antibacterial compounds. Here, we report the development of a semiquantitative mass spectrometry-based assay for kinetic characterization of LanM-catalyzed reactions. The assay was used to conduct a comparative kinetic analysis of two LanM enzymes (HalM2 and ProcM) that exhibit drastically different substrate selectivity. Numerical simulation of the kinetic data was used to develop models for the multistep HalM2- and ProcM-catalyzed reactions. These models illustrate that HalM2 and ProcM have markedly different catalytic efficiencies for the various reactions they catalyze. HalM2, which is responsible for the biosynthesis of a single compound (the Halβ subunit of the lantibiotic haloduracin), catalyzes reactions with higher catalytic efficiency than ProcM, which modifies 29 different ProcA precursor peptides during prochlorosin biosynthesis. In particular, the rates of thioether ring formation are drastically reduced in ProcM, likely because this enzyme is charged with installing a variety of lanthipeptide ring architectures in its prochlorosin products. Thus, ProcM appears to pay a kinetic price for its relaxed substrate specificity. In addition, our kinetic models suggest that conformational sampling of the LanM/LanA Michaelis complex could play an important role in the kinetics of LanA maturation. PMID:25409537

Enzymatic synthesis of chiral amino‐alcohols by coupling transketolase and transaminase‐catalyzed reactions in a cascading continuous‐flow microreactor system

PubMed Central

Gruber, Pia; Carvalho, Filipe; Marques, Marco P. C.; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C.; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank

2017-01-01

Abstract Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino‐alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)‐2‐amino‐1,3,4‐butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non‐chiral starting materials, by coupling a transketolase‐ and a transaminase‐catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor‐based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous‐flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase‐catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml−1. Following optimization of the transaminase‐catalyzed reaction, a volumetric activity of 10.8 U ml−1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous‐flow microreactors can be applied for the design and optimization of biocatalytic processes. PMID:28986983

Synthesis of 2-monoacylglycerols and structured triacylglycerols rich in polyunsaturated fatty acids by enzyme catalyzed reactions.

PubMed

Rodríguez, Alicia; Esteban, Luis; Martín, Lorena; Jiménez, María José; Hita, Estrella; Castillo, Beatriz; González, Pedro A; Robles, Alfonso

2012-08-10

This paper studies the synthesis of structured triacylglycerols (STAGs) by a four-step process: (i) obtaining 2-monoacylglycerols (2-MAGs) by alcoholysis of cod liver oil with several alcohols, catalyzed by lipases Novozym 435, from Candida antartica and DF, from Rhizopus oryzae, (ii) purification of 2-MAGs, (iii) formation of STAGs by esterification of 2-MAGs with caprylic acid catalyzed by lipase DF, from R. oryzae, and (iv) purification of these STAGs. For the alcoholysis of cod liver oil, absolute ethanol, ethanol 96% (v/v) and 1-butanol were compared; the conditions with ethanol 96% were then optimized and 2-MAG yields of around 54-57% were attained using Novozym 435. In these 2-MAGs, DHA accounted for 24-31% of total fatty acids. In the operational conditions this lipase maintained a stable level of activity over at least 11 uses. These results were compared with those obtained with lipase DF, which deactivated after only three uses. The alcoholysis of cod liver oil and ethanol 96% catalyzed by Novozym 435 was scaled up by multiplying the reactant amounts 100-fold and maintaining the intensity of treatment constant (IOT=3g lipase h/g oil). In these conditions, the 2-MAG yield attained was about 67%; these 2-MAGs contained 36.6% DHA. The synthesized 2-MAGs were separated and purified from the alcoholysis reaction products by solvent extraction using solvents of low toxicity (ethanol and hexane); 2-MAG recovery yield and purity of the target product were approximately 96.4% and 83.9%, respectively. These 2-MAGs were transformed to STAGs using the optimal conditions obtained in a previous work. After synthesis and purification, 93% pure STAGs were obtained, containing 38% DHA at sn-2 position and 60% caprylic acid (CA) at sn-1,3 positions (of total fatty acids at these positions), i.e. the major TAG is the STAG with the structure CA-DHA-CA. Copyright © 2012 Elsevier Inc. All rights reserved.

Rhodium-Catalyzed Denitrogenative [3+2] Cycloaddition: Access to Functionalized Hydroindolones and the Framework of Montanine-Type Amaryllidaceae Alkaloids.

PubMed

Yang, Hongjian; Hou, Shengtai; Tao, Cheng; Liu, Zhao; Wang, Chao; Cheng, Bin; Li, Yun; Zhai, Hongbin

2017-09-18

Rhodium-catalyzed denitrogenative [3+2] cycloaddition of 1-sulfonyl-1,2,3-triazoles with cyclic silyl dienol ethers has been developed for the synthesis of functionalized hydroindolones or their corresponding silyl ethers. The present method has been employed to construct synthetically valuable bicyclo[3.3.1]alkenone derivatives and pyrrolidine-ring-containing bicyclic indole compounds. As a further synthetic application, a stereoselective synthesis of 5,11-methanomorphanthridin-3-one, which shares a key skeleton with montanine-type Amaryllidaceae alkaloids has been achieved by using this chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.

PubMed

Ratani, Tanvi S; Bachman, Shoshana; Fu, Gregory C; Peters, Jonas C

2015-11-04

We have recently reported that, in the presence of light and a copper catalyst, nitrogen nucleophiles such as carbazoles and primary amides undergo C-N coupling with alkyl halides under mild conditions. In the present study, we establish that photoinduced, copper-catalyzed alkylation can also be applied to C-C bond formation, specifically, that the cyanation of unactivated secondary alkyl chlorides can be achieved at room temperature to afford nitriles, an important class of target molecules. Thus, in the presence of an inexpensive copper catalyst (CuI; no ligand coadditive) and a readily available light source (UVC compact fluorescent light bulb), a wide array of alkyl halides undergo cyanation in good yield. Our initial mechanistic studies are consistent with the hypothesis that an excited state of [Cu(CN)2](-) may play a role, via single electron transfer, in this process. This investigation provides a rare example of a transition metal-catalyzed cyanation of an alkyl halide, as well as the first illustrations of photoinduced, copper-catalyzed alkylation with either a carbon nucleophile or a secondary alkyl chloride.

Room-temperature chromium(II)-catalyzed direct arylation of pyridines, aryl oxazolines, and imines using arylmagnesium reagents.

PubMed

Kuzmina, Olesya M; Knochel, Paul

2014-10-03

We report a CrCl2-catalyzed oxidative arylation of various pyridines, aryl oxazolines, and aryl imines using aromatic Grignard reagents in the presence of 2,3-dichlorobutane (DCB). Most of the reactions proceed rapidly at 25 °C and do not require any additional ligand. Benzo[h]quinoline, 2-arylpyridine, aryl oxazoline, and imines were successfully arylated in good yields under these conditions. A TMS-substituent was used to prevent double arylation. After oxidative cross-coupling the TMS-group was further converted to a second ortho-aryl substituent. Remarkably, inexpensive aryl N-butylimine derivatives are excellent substrates for this oxidative arylation.

Copper-Catalyzed C(sp2)-S Coupling Reactions for the Synthesis of Aryl Dithiocarbamates with Thiuram Disulfide Reagents.

PubMed

Dong, Zhi-Bing; Liu, Xing; Bolm, Carsten

2017-11-03

An efficient protocol for the copper-catalyzed preparation of aryl dithiocarbamates from aryl iodides and inexpensive, environmentally benign tetraalkylthiuram disulfides was developed. The features of mild reaction conditions, high yields, and broad substrate scope render this new approach synthetically attractive for the preparation of potentially biologically active compounds.

General synthesis of C-glycosyl amino acids via proline-catalyzed direct electrophilic alpha-amination of C-glycosylalkyl aldehydes.

PubMed

Nuzzi, Andrea; Massi, Alessandro; Dondoni, Alessandro

2008-10-16

Non-natural axially and equatorially linked C-glycosyl alpha-amino acids (glycines, alanines, and CH2-serine isosteres) with either S or R alpha-configuration were prepared by D- and L-proline-catalyzed (de >95%) alpha-amination of C-glycosylalkyl aldehydes using dibenzyl azodicarboxylate as the electrophilic reagent.

Pd(OAc)2-Catalyzed Domino Reactions of 1-Chloro-2-Haloarenes and 2-Haloaryl Tosylates with Hindered Grignard Reagents via Palladium Associated Arynes

PubMed Central

Dong, Cheng-Guo; Hu, Qiao-Sheng

2008-01-01

The palladium associated aryne generation strategy and Pd(OAc)2-catalyzed annulative Domino reactions of 1-chloro-2-halobenzenes and 2-haloaryl tosylates with hindered Grignard reagents via palladium associated arynes are described. The palladium associated aryne generation strategy described here not only allows the high yield, one-step access to potentially useful substituted fluorenes from readily available 1-chloro-2-halobenzenes and 2-haloaryl tosylates, but may also lead to the development of other tandem reactions based on these readily available o-leaving group bearing haloarenes PMID:17048842

Pd(OAc)(2)-catalyzed Domino reactions of 1-chloro-2-haloarenes and 2-haloaryl tosylates with hindered Grignard reagents via palladium-associated arynes.

PubMed

Dong, Cheng-Guo; Hu, Qiao-Sheng

2006-10-26

The palladium-associated aryne generation strategy and Pd(OAc)(2)-catalyzed annulative Domino reactions of 1-chloro-2-halobenzenes and 2-haloaryl tosylates with hindered Grignard reagents via palladium-associated arynes are described. The palladium-associated aryne generation strategy described here not only allows the high yield, one-step access to potentially useful substituted fluorenes from readily available 1-chloro-2-halobenzenes and 2-haloaryl tosylates, but may also lead to the development of other tandem reactions based on these readily available ortho leaving group bearing haloarenes. [reaction: see text

Rhodium-catalyzed sequential allylic amination and olefin hydroacylation reactions: enantioselective synthesis of seven-membered nitrogen heterocycles.

PubMed

Arnold, Jeffrey S; Mwenda, Edward T; Nguyen, Hien M

2014-04-01

Dynamic kinetic asymmetric amination of branched allylic acetimidates has been applied to the synthesis of 2-alkyl-dihydrobenzoazepin-5-ones. These seven-membered-ring aza ketones are prepared in good yield with high enantiomeric excess by rhodium-catalyzed allylic substitution with 2-amino aryl aldehydes followed by intramolecular olefin hydroacylation of the resulting alkenals. This two-step procedure is amenable to varied functionality and proves useful for the enantioselective preparation of these ring systems. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced removal of aqueous acetaminophen by a laccase-catalyzed oxidative coupling reaction under a dual-pH optimization strategy.

PubMed

Wang, Kaidong; Huang, Ke; Jiang, Guoqiang

2018-03-01

Acetaminophen is one kind of pharmaceutical contaminant that has been detected in municipal water and is hard to digest. A laccase-catalyzed oxidative coupling reaction is a potential method of removing acetaminophen from water. In the present study, the kinetics of radical polymerization combined with precipitation was studied, and the dual-pH optimization strategy (the enzyme solution at pH7.4 being added to the substrate solution at pH4.2) was proposed to enhance the removal efficiency of acetaminophen. The reaction kinetics that consisted of the laccase-catalyzed oxidation, radical polymerization and precipitation were studied by UV in situ, LC-MS and DLS (dynamic light scattering) in situ. The results showed that the laccase-catalyzed oxidation is the rate-limiting step in the whole process. The higher rate of enzyme-catalyzed oxidation under a dual-pH optimization strategy led to much faster formation of the dimer, trimer and tetramer. Similarly, the formation of polymerized products that could precipitate naturally from water was faster. Under the dual-pH optimization strategy, the initial laccase activity was increased approximately 2.9-fold, and the activity remained higher for >250s, during which approximately 63.7% of the total acetaminophen was transformed into biologically inactive polymerized products, and part of these polymerized products precipitated from the water. Laccase belongs to the family of multi-copper oxidases, and the present study provides a universal method to improve the activity of multi-copper oxidases for the high-performance removal of phenol and its derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Cloning and Functional Characterization of Three Distinct N-Methyltransferases Involved in the Caffeine Biosynthetic Pathway in Coffee Plants1

PubMed Central

Uefuji, Hirotaka; Ogita, Shinjiro; Yamaguchi, Yube; Koizumi, Nozomu; Sano, Hiroshi

2003-01-01

Caffeine is synthesized from xanthosine through N-methylation and ribose removal steps. In the present study, three types of cDNAs encoding N-methyltransferases were isolated from immature fruits of coffee (Coffea arabica) plants, and designated as CaXMT1, CaMXMT2, and CaDXMT1, respectively. The bacterially expressed encoded proteins were characterized for their catalytic properties. CaXMT1 catalyzed formation of 7-methylxanthosine from xanthosine with a Km value of 78 μm, CaMXMT2 catalyzed formation of 3,7-dimethylxanthine (theobromine) from 7-methylxanthine with a Km of 251 μm, and CaDXMT1 catalyzed formation of 1,3,7-trimethylxanthine (caffeine) from 3,7-dimethylxanthine with a Km of 1,222 μm. The crude extract of Escherichia coli was found to catalyze removal of the ribose moiety from 7-methylxanthosine, leading to the production of 7-methylxanthine. As a consequence, when all three recombinant proteins and E. coli extract were combined, xanthosine was successfully converted into caffeine in vitro. Transcripts for CaDXMT1 were predominantly found to accumulate in immature fruits, whereas those for CaXMT1 and CaMXMT2 were more broadly detected in sites encompassing the leaves, floral buds, and immature fruits. These results suggest that the presently identified three N-methyltransferases participate in caffeine biosynthesis in coffee plants and substantiate the proposed caffeine biosynthetic pathway: xanthosine → 7-methylxanthosine → 7-methylxanthine → theobromine → caffeine. PMID:12746542

Extreme halophilic alcohol dehydrogenase mediated highly efficient syntheses of enantiopure aromatic alcohols.

PubMed

Alsafadi, Diya; Alsalman, Safaa; Paradisi, Francesca

2017-11-07

Enzymatic synthesis of enantiopure aromatic secondary alcohols (including substituted, hetero-aromatic and bicyclic structures) was carried out using halophilic alcohol dehydrogenase ADH2 from Haloferax volcanii (HvADH2). This enzyme showed an unprecedented substrate scope and absolute enatioselectivity. The cofactor NADPH was used catalytically and regenerated in situ by the biocatalyst, in the presence of 5% ethanol. The efficiency of HvADH2 for the conversion of aromatic ketones was markedly influenced by the steric and electronic factors as well as the solubility of ketones in the reaction medium. Furthermore, carbonyl stretching band frequencies ν (C[double bond, length as m-dash]O) have been measured for different ketones to understand the effect of electron withdrawing or donating properties of the ketone substituents on the reaction rate catalyzed by HvADH2. Good correlation was observed between ν (C[double bond, length as m-dash]O) of methyl aryl-ketones and the reaction rate catalyzed by HvADH2. The enzyme catalyzed the reductions of ketone substrates on the preparative scale, demonstrating that HvADH2 would be a valuable biocatalyst for the preparation of chiral aromatic alcohols of pharmaceutical interest.

Recent Development in Chemical Depolymerization of Lignin: A Review

DOE PAGES

Wang, Hai; Tucker, Melvin; Ji, Yun

2013-01-01

This article reviewed recent development of chemical depolymerization of lignins. There were five types of treatment discussed, including base-catalyzed, acid-catalyzed, metallic catalyzed, ionic liquids-assisted, and supercritical fluids-assisted lignin depolymerizations. The methods employed in this research were described, and the important results were marked. Generally, base-catalyzed and acid-catalyzed methods were straightforward, but the selectivity was low. The severe reaction conditions (high pressure, high temperature, and extreme pH) resulted in requirement of specially designed reactors, which led to high costs of facility and handling. Ionic liquids, and supercritical fluids-assisted lignin depolymerizations had high selectivity, but the high costs of ionic liquids recyclingmore » and supercritical fluid facility limited their applications on commercial scale biomass treatment. Metallic catalyzed depolymerization had great advantages because of its high selectivity to certain monomeric compounds and much milder reaction condition than base-catalyzed or acid-catalyzed depolymerizations. It would be a great contribution to lignin conversion if appropriate catalysts were synthesized.« less

A SABATH Methyltransferase from the moss Physcomitrella patens catalyzes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Nan; Ferrer, Jean-Luc; Moon, Hong S

2012-01-01

Known SABATH methyltransferases, all of which were identified from seed plants, catalyze methylation of either the carboxyl group of a variety of low molecular weight metabolites or the nitrogen moiety of precursors of caffeine. In this study, the SABATH family from the bryophyte Physcomitrella patens was identified and characterized. Four SABATH-like sequences (PpSABATH1, PpSABATH2, PpSABATH3, and PpSABATH4) were identified from the P. patens genome. Only PpSABATH1 and PpSABATH2 showed expression in the leafy gametophyte of P. patens. Full-length cDNAs of PpSABATH1 and PpSABATH2 were cloned and expressed in soluble form in Escherichia coli. Recombinant PpSABATH1 and PpSABATH2 were tested formore » methyltransferase activity with a total of 75 compounds. While showing no activity with carboxylic acids or nitrogen-containing compounds, PpSABATH1 displayed methyltransferase activity with a number of thiols. PpSABATH2 did not show activity with any of the compounds tested. Among the thiols analyzed, PpSABATH1 showed the highest level of activity with thiobenzoic acid with an apparent Km value of 95.5 lM, which is comparable to those of known SABATHs. Using thiobenzoic acid as substrate, GC MS analysis indicated that the methylation catalyzed by PpSABATH1 is on the sulfur atom. The mechanism for S-methylation of thiols catalyzed by PpSABATH1 was partially revealed by homology-based structural modeling. The expression of PpSABATH1 was induced by the treatment of thiobenzoic acid. Further transgenic studies showed that tobacco plants overexpressing PpSABATH1 exhibited enhanced tolerance to thiobenzoic acid, suggesting that PpSABATH1 have a role in the detoxification of xenobiotic thiols.« less

Non-aggregation based label free colorimetric sensor for the detection of Cu2+ based on catalyzing etching of gold nanorods by dissolve oxygen.

PubMed

Liu, Jia-Ming; Jiao, Li; Lin, Li-Ping; Cui, Ma-Lin; Wang, Xin-Xing; Zhang, Li-Hong; Zheng, Zhi-Yong; Jiang, Shu-Lian

2013-12-15

A label-free non-aggregation colorimetric sensor has been designed for the detection of Cu(2+), based on Cu(2+) catalyzing etching of gold nanorods (AuNRs) along longitudinal axis induced by dissolve oxygen in the presence of S2O3(2-), which caused the aspect ratio (length/width) of AuNRs to decrease and the color of the solution to distinctly change. The linear range and the detection limit (LD, calculated by 10 Sb/k, n=11) of this sensor were 0.080-4.8 µM Cu(2+) and 0.22 µM Cu(2+), respectively. This sensor has been utilized to detect Cu(2+) in tap water and human serum samples with the results agreeing well with those of inductively coupled plasma-mass spectroscopy (ICP-MS), showing its remarkable practicality. In order to prove the possibility of catalyzing AuNRs non-aggregation colorimetric sensor for the detection of Cu(2+), the morphological structures of AuNRs were characterized by high resolution transmission electron microscopy (HRTEM) and the sensing mechanism of colorimetric sensor for the detection of Cu(2+) was also discussed. © 2013 Elsevier B.V. All rights reserved.

Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

DOE PAGES

Morgan, Gregg A.; Xiao, S. Xin

2015-03-06

The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H 2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D 2O, leaving H 2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminatedmore » water (T 2O, HTO, and DTO) using D 2 (or H 2)« less

Heterogeneous UV/Fenton degradation of bisphenol A catalyzed by synergistic effects of FeCo2O4/TiO2/GO.

PubMed

Bai, Xue; Lyu, Lingling; Ma, Wenqiang; Ye, Zhengfang

2016-11-01

A new method for bisphenol A (BPA) degradation in aqueous solution was developed. The characteristics of BPA degradation in a heterogeneous ultraviolet (UV)/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /graphite oxide (GO) were studied. The properties of the synthesized catalysts were characterized using scanning electron microscopy, X-ray diffraction, and vibrating sample magnetometry. FeCo 2 O 4 and TiO 2 were grown as spherical shape, rough surface, and relatively uniform on the surface of GO (FeCo 2 O 4 /TiO 2 /GO). Batch tests were conducted to evaluate the effects of the initial pH, FeCo 2 O 4 /TiO 2 /GO dosage, and H 2 O 2 concentration on BPA degradation. In a system with 0.5 g L -1 of FeCo 2 O 4 /TiO 2 /GO and 10 mmol L -1 of H 2 O 2 , approximately 90 % of BPA (20 mg L -1 ) was degraded within 240 min of UV irradiation at pH 6.0. The reused FeCo 2 O 4 /TiO 2 /GO catalyst retained its activity after three cycles, which indicates that it is stable and reusable. The heterogeneous UV/Fenton reaction catalyzed by FeCo 2 O 4 /TiO 2 /GO is a promising advanced oxidation technology for treating wastewater that contains BPA.

Stereodivergent Synthesis of N-Heterocycles by Catalyst-Controlled, Activity-Directed Tandem Annulation of Diazo Compounds with Amino Alkynes.

PubMed

Liu, Kai; Zhu, Chenghao; Min, Junxiang; Peng, Shiyong; Xu, Guangyang; Sun, Jiangtao

2015-10-26

A stereodivergent synthesis of five-membered N-heterocycles, such as 2,3-dihydropyrroles, and 2-methylene and 3-methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper-catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium-catalyzed protocol features a carbenoid insertion into the NH bond and subsequent Conia-ene cyclization. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bacterial Conversion of Hydroxylamino Aromatic Compounds by both Lyase and Mutase Enzymes Involves Intramolecular Transfer of Hydroxyl Groups

PubMed Central

Nadeau, Lloyd J.; He, Zhongqi; Spain, Jim C.

2003-01-01

Hydroxylamino aromatic compounds are converted to either the corresponding aminophenols or protocatechuate during the bacterial degradation of nitroaromatic compounds. The origin of the hydroxyl group of the products could be the substrate itself (intramolecular transfer mechanism) or the solvent water (intermolecular transfer mechanism). The conversion of hydroxylaminobenzene to 2-aminophenol catalyzed by a mutase from Pseudomonas pseudoalcaligenes JS45 proceeds by an intramolecular hydroxyl transfer. The conversions of hydroxylaminobenzene to 2- and 4-aminophenol by a mutase from Ralstonia eutropha JMP134 and to 4-hydroxylaminobenzoate to protocatechuate by a lyase from Comamonas acidovorans NBA-10 and Pseudomonas sp. strain 4NT were proposed, but not experimentally proved, to proceed by the intermolecular transfer mechanism. GC-MS analysis of the reaction products formed in H218O did not indicate any 18O-label incorporation during the conversion of hydroxylaminobenzene to 2- and 4-aminophenols catalyzed by the mutase from R. eutropha JMP134. During the conversion of 4-hydroxylaminobenzoate catalyzed by the hydroxylaminolyase from Pseudomonas sp. strain 4NT, only one of the two hydroxyl groups in the product, protocatechuate, was 18O labeled. The other hydroxyl group in the product must have come from the substrate. The mutase in strain JS45 converted 4-hydroxylaminobenzoate to 4-amino-3-hydroxybenzoate, and the lyase in Pseudomonas strain 4NT converted hydroxylaminobenzene to aniline and 2-aminophenol but not to catechol. The results indicate that all three types of enzyme-catalyzed rearrangements of hydroxylamino aromatic compounds proceed via intramolecular transfer of hydroxyl groups. PMID:12732549

A dual nitrite isotopic investigation of chemodenitrification by mineral-associated Fe(II) and its production of nitrous oxide

NASA Astrophysics Data System (ADS)

Grabb, Kalina C.; Buchwald, Carolyn; Hansel, Colleen M.; Wankel, Scott D.

2017-01-01

Under anaerobic conditions, the environmental reduction of nitrate (NO3-) and nitrite (NO2-) to more reduced forms is widely regarded as being microbially catalyzed. However, the chemical reduction of oxidized nitrogen species by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under environmentally relevant conditions. Here we examine the nitrogen (N) and oxygen (O) stable isotope dynamics of the chemical reduction of NO2- by mineral associated Fe(II) (chemodenitrification) and its production of the potent greenhouse gas nitrous oxide (N2O). By shedding light on factors controlling kinetics of the reaction and its corresponding dual isotopic expression in the reactant NO2- and product N2O, this work contributes to a growing body of work aiming to improve our ability to identify chemodenitrification in the environment. Consistent with previous studies, we find that while homogenous reactions between aqueous NO2- and Fe(II) were kinetically slow, heterogeneous reactions involving Fe(II)-containing minerals often catalyzed considerable nitrite loss. In particular, rapid reduction of NO2- was catalyzed by the Fe-rich smectite clay mineral nontronite as well as the mixed Fe(II)-Fe(III) oxyhydroxide phase green rust. These minerals serve as both a source of reduced iron within the mineral structure as well as a surface for promoting the reactivity of Fe(II). However, even in the presence of aqueous Fe(II), experiments with low-Fe and non-Fe containing minerals showed little to no NO2- loss, perhaps suggesting a more dominant role for structural iron during chemodenitrification. When catalyzed by nontronite and green rust, N and O isotope effects for chemodenitrification (15εcDNF and 18εcDNF) ranged from 2 to 11‰ and 4 to 10‰, respectively, with lower values generally observed at higher reaction rates. Higher reaction rates were also linked to higher molar yields of N2O (up to 31%), highlighting a strong potential for chemodenitrification to produce N2O - especially relative to its production by microbial pathways, which typically exhibit yields <1%. The intramolecular 15N site preference (SP) of the linear N2O molecule (the difference in δ15N between the central and outer atoms), reflective of different production mechanisms, was also measured for N2O produced during green rust catalyzed chemodenitrification. Relative to values measured in other recent studies of chemodenitrification, SP values were consistently high (+26.5‰ ± 0.8‰), especially relative to N2O produced via bacterial denitrification (SP ∼ 0‰). Finally, the coupling of 18εcDNF and 15εcDNF at a ratio of ∼1 during green rust catalyzed chemodenitrification contrasts distinctly with recently characterized bacterial nitrite reduction, potentially permitting disentangling of both processes under well-constrained conditions. This study contributes to the broader understanding of the potential relevance for mineral-derived Fe(II) to promote the reduction of nitrite and consequent production of N2O, especially in iron-rich systems hosting dynamic redox oscillations, including hyporheic zones, estuarine sediments and groundwater aquifers.

Probing the importance of the hemilabile site of bis(phosphine) monoxide ligands in the copper-catalyzed addition of diethylzinc to N-phosphinoylimines: discovery of new effective chiral ligands.

PubMed

Bonnaventure, Isabelle; Charette, André B

2008-08-15

The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding alpha-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu* 2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of beta,beta-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.

Revisiting the substrate specificity of mammalian α1,6-fucosyltransferase reveals that it catalyzes core fucosylation of N-glycans lacking α1,3-arm GlcNAc.

PubMed

Yang, Qiang; Zhang, Roushu; Cai, Hui; Wang, Lai-Xi

2017-09-08

The mammalian α1,6-fucosyltransferase (FUT8) catalyzes the core fucosylation of N -glycans in the biosynthesis of glycoproteins. Previously, intensive in vitro studies with crude extract or purified enzyme concluded that the attachment of a GlcNAc on the α1,3 mannose arm of N -glycan is essential for FUT8-catalyzed core fucosylation. In contrast, we have recently shown that expression of erythropoietin in a GnTI knock-out, FUT8-overexpressing cell line results in the production of fully core-fucosylated glycoforms of the oligomannose substrate Man 5 GlcNAc 2 , suggesting that FUT8 can catalyze core fucosylation of N -glycans lacking an α1,3-arm GlcNAc in cells. Here, we revisited the substrate specificity of FUT8 by examining its in vitro activity toward an array of selected N -glycans, glycopeptides, and glycoproteins. Consistent with previous studies, we found that free N -glycans lacking an unmasked α1,3-arm GlcNAc moiety are not FUT8 substrates. However, Man 5 GlcNAc 2 glycan could be efficiently core-fucosylated by FUT8 in an appropriate protein/peptide context, such as with the erythropoietin protein, a V3 polypeptide derived from HIV-1 gp120, or a simple 9-fluorenylmethyl chloroformate-protected Asn moiety. Interestingly, when placed in the V3 polypeptide context, a mature bi-antennary complex-type N -glycan also could be core-fucosylated by FUT8, albeit at much lower efficiency than the Man 5 GlcNAc 2 peptide. This study represents the first report of in vitro FUT8-catalyzed core fucosylation of N -glycans lacking the α1,3-arm GlcNAc moiety. Our results suggest that an appropriate polypeptide context or other adequate structural elements in the acceptor substrate could facilitate the core fucosylation by FUT8. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Rhodium(i)-catalyzed asymmetric [4 + 2] cycloaddition reactions of 2-alkylenecyclobutanols with cyclic enones through C–C bond cleavage: efficient access to trans-bicyclic compounds† †Electronic supplementary information (ESI) available. CCDC 1575240. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc04784c

PubMed Central

Zheng, Xinxin; Guo, Rui

2018-01-01

We report a rhodium-catalyzed asymmetric formal intermolecular [4 + 2] cycloaddition reaction of 2-alkylenecyclobutanols with α,β-unsaturated cyclic ketones leading to synthetically useful trans-bicyclic molecules. Three consecutive stereogenic centers are formed in a highly enantio- and diastereoselective manner. Stepwise C–C bond cleavage and annulation are likely involved in the reaction pathway. Here, iPr-Duphos is the viable chiral ligand that promotes excellent enantio-control. PMID:29675233

Synthesis of π-conjugated polymer consisting of pyrrole and fluorene units by Ru-catalyzed site-selective direct arylation polycondensation.

PubMed

Lu, Wei; Kuwabara, Junpei; Kanbara, Takaki

2013-07-25

Polycondensation of 1-(2-pyrimidinyl)pyrrole with 2,7-dibromo-9,9-dioctylfluorene via Ru-catalyzed direct arylation gives the corresponding conjugated polymer with a molecular weight of 19 800 in 86% yield. The introduction of directing group, 2-pyrimidinyl substituent, into the pyrrole monomer induces ortho-metalation and provides the site-selective direct arylation polycondensation at the α-position of pyrrole unit without the protection of β-position. The removal of 2-pyrimidinyl substituent on the pyrrole unit proceeds efficiently and results in the enhancement of coplanarity along the main chain of the polymer. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Yield of 1,6-anhydro-3,4-dideoxy-β-D-glycero-hex-3-enopyranos-2-ulose (levoglucosenone) on the acid-catalyzed pyrolysis of cellulose and 1,6-anhydro-β-D-glucopyranose (levoglucosan)

Treesearch

Abraham Broido; Malcolm Evett; Craig C. Hodges

1975-01-01

Although 1,6-anhydro-3,4-dideoxy-β-D-glycero-hex-3-enopyranos-2-ulose (2) is produced by the acid-catalyzed pyrolysis of both cellulose and 1,6-anhydro-β-D-glucopyranose (1), data presented here show that the principal mechanism of its formation in the pyrolysis of cellulose is not via 1. Furthermore, the data provide evidence that 1 itself is not...

Iron-catalyzed stereospecific activation of olefinic C-H bonds with Grignard reagent for synthesis of substituted olefins.

PubMed

Ilies, Laurean; Asako, Sobi; Nakamura, Eiichi

2011-05-25

The reaction of an aryl Grignard reagent with a cyclic or acyclic olefin possessing a directing group such as pyridine or imine results in the stereospecific substitution of the olefinic C-H bond syn to the directing group. The reaction takes place smoothly and without isomerization of the product olefin in the presence of a mild oxidant (1,2-dichloro-2-methylpropane) and an aromatic cosolvent. Several lines of evidence suggest that the reaction proceeds via iron-catalyzed olefinic C-H bond activation rather than an oxidative Mizoroki-Heck-type reaction.

Tandem catalytic allylic amination and [2,3]-Stevens rearrangement of tertiary amines.

PubMed

Soheili, Arash; Tambar, Uttam K

2011-08-24

We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

Enantioselective Organocatalytic Aminomethylation of Aldehydes: A Role for Ionic Interactions and Efficient Access to β2-Amino Acids

PubMed Central

Chi, Yonggui; Gellman, Samuel H.

2009-01-01

Organocatalytic Mannich addition of aldehydes to a formaldehyde-derived iminium species catalyzed by proline-derived chiral pyrrolidines provides β-amino aldehydes with ≥ 90% ee. Mechanistic analysis of the proline-catalyzed reactions suggests that non-hydrogen-bonded ionic interactions at the Mannich reaction transition state can influence stereochemical outcome. The β-amino aldehydes from our process bear a substituent adjacent to the carbonyl and can be efficiently converted to protected β2-amino acids, which are important building blocks for β-peptide foldamers that display useful biological activities. PMID:16719457

Atomically dispersed Au-(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction.

PubMed

Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

2013-03-13

We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au-O-TiO(x) sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this "excess" gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

Click chemistry-mediated cyclic cleavage of metal ion-dependent DNAzymes for amplified and colorimetric detection of human serum copper (II).

PubMed

Li, Daxiu; Xie, Jiaqing; Zhou, Wenjiao; Jiang, Bingying; Yuan, Ruo; Xiang, Yun

2017-11-01

The determination of the level of Cu 2+ plays important roles in disease diagnosis and environmental monitoring. By coupling Cu + -catalyzed click chemistry and metal ion-dependent DNAzyme cyclic amplification, we have developed a convenient and sensitive colorimetric sensing method for the detection of Cu 2+ in human serums. The target Cu 2+ can be reduced by ascorbate to form Cu + , which catalyzes the azide-alkyne cycloaddition between the azide- and alkyne-modified DNAs to form Mg 2+ -dependent DNAzymes. Subsequently, the Mg 2+ ions catalyze the cleavage of the hairpin DNA substrate sequences of the DNAzymes and trigger cyclic generation of a large number of free G-quadruplex sequences, which bind hemin to form the G-quadruplex/hemin artificial peroxidase to cause significant color transition of the sensing solution for sensitive colorimetric detection of Cu 2+ . This method shows a dynamic range of 5 to 500 nM and a detection limit of 2 nM for Cu 2+ detection. Besides, the level of Cu 2+ in human serums can also be determined by using this sensing approach. With the advantages of simplicity and high sensitivity, such sensing method thus holds great potential for on-site determination of Cu 2+ in different samples. Graphical abstract Sensitive colorimetric detection of copper (II) by coupling click chemistry with metal ion-dependentDNAzymes.

Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

PubMed

Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

2015-10-05

An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 2-Azulenyltetrathiafulvalenes by Palladium-Catalyzed Direct Arylation of 2-Chloroazulenes with Tetrathiafulvalene and Their Optical and Electrochemical Properties.

PubMed

Shoji, Taku; Araki, Takanori; Sugiyama, Shuhei; Ohta, Akira; Sekiguchi, Ryuta; Ito, Shunji; Okujima, Tetsuo; Toyota, Kozo

2017-02-03

Tetrathiafulvalene (TTF) derivatives with 2-azulenyl substituents 5-11 were prepared by the palladium-catalyzed direct arylation reaction of 2-chloroazulenes with TTF in good yield. Photophysical properties of these compounds were investigated by UV-vis spectroscopy and theoretical calculations. Redox behavior of the novel azulene-substituted TTFs was examined by using cyclic voltammetry and differential pulse voltammetry, which revealed their multistep electrochemical oxidation and/or reduction properties. Moreover, these TTF derivatives showed significant spectral change in the visible region under the redox conditions.

Brönsted Acid-Catalyzed One-Pot Synthesis of Indoles from o-Aminobenzyl Alcohols and Furans

PubMed Central

Kuznetsov, Alexey; Makarov, Anton; Rubtsov, Alexandr E.; Butin, Alexander V.; Gevorgyan, Vladimir

2013-01-01

Brönsted acid-catalyzed one-pot synthesis of indoles from o-aminobenzyl alcohols and furans has been developed. This method operates via the in situ formation of aminobenzylfuran, followed by its recyclization into the indole core. The method proved to be efficient for substrates possessing different functional groups, including -OMe, -CO2Cy, and -Br. The resulting indoles can easily be transformed into diverse scaffolds, including 2,3- and 1,2-fused indoles, and indole possessing an α,β-unsaturated ketone moiety at the C-2 position. PMID:24255969

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

DOE PAGES

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

2017-10-27

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

Lewis acid catalysis and ligand exchange in the asymmetric binaphthol-catalyzed propargylation of ketones.

PubMed

Grayson, Matthew N; Goodman, Jonathan M

2013-09-06

1,1'-Bi-2-naphthol (BINOL)-derived catalysts catalyze the asymmetric propargylation of ketones. Density functional theory (DFT) calculations show that the reaction proceeds via a closed six-membered transition structure (TS) in which the chiral catalyst undergoes an exchange process with the original cyclic boronate ligand. This leads to a Lewis acid type activation mode, not a Brønsted acid process, which accurately predicts the stereochemical outcome observed experimentally.

A catalytic borylation/dehalogenation route to o-fluoro arylboronates.

PubMed

Jayasundara, Chathurika R K; Unold, Jason M; Oppenheimer, Jossian; Smith, Milton R; Maleczka, Robert E

2014-12-05

A two-step Ir-catalyzed borylation/Pd-catalyzed dehalogenation sequence allows for the net synthesis of fluoroarenes where the boronic ester is ortho to fluorine. Key elements of this approach include the use of a halogen para to the fluorine to block meta Ir-catalyzed borylation and the chemoselective Pd-catalyzed dehalogenation by KF activated polymethylhydrosiloxane (PMHS).

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

PubMed

Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

2016-05-17

Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in solving complex problems and proposing new detailed reaction mechanisms that rationalize the experimental findings. For each of the considered reactions, a consistent mechanism is presented, the experimentally observed selectivities are reproduced, and their sources are identified. Reproducing selectivities requires high accuracy in computing relative transition state energies. As demonstrated by the results summarized in this Account, this accuracy is possible with the use of the presented methodology, benefiting of course from a large extent of cancellation of systematic errors. It is argued that as the employed models become larger, the number of rotamers and isomers that have to be considered for every stationary point increases and a careful assessment of their energies is therefore necessary in order to ensure that the lowest energy conformation is located. This issue constitutes a bottleneck of the investigation in some cases and is particularly important when analyzing selectivities, since small energy differences need to be reproduced.

γ-Alumina Nanoparticle Catalyzed Efficient Synthesis of Highly Substituted Imidazoles.

PubMed

Reddy, Bandapalli Palakshi; Vijayakumar, Vijayaparthasarathi; Arasu, Mariadhas Valan; Al-Dhabi, Naif Abdullah

2015-10-21

γ-Alumina nano particle catalyzed multi component reaction of benzil, arylaldehyde and aryl amines afforded the highly substituted 1,2,4,5-tetraaryl imidazoles with good to excellent yield in less reaction time under the sonication as well as the conventional methods. Convenient operational simplicity, mild conditions and the reusability of catalyst were the other advantages of this developed protocol.

Lewis base catalyzed 1,3-dithiane addition to carbonyl and imino compounds using 2-trimethylsilyl-1,3-dithiane.

PubMed

Michida, Makoto; Mukaiyama, Teruaki

2008-09-01

Lewis base-catalyzed 1,3-dithiane addition to electrophiles such as carbonyl compounds and N-substituted aldimines with 2-trimethylsilyl-1,3-dithiane (TMS-dithiane) is described. By the activation of the carbon-silicon bond in the presence of a Lewis base catalyst such as tetrabutylammonium phenoxide (PhONnBu(4)), a 1,3-dithiane addition reaction proceeded smoothly to afford the corresponding adducts in good to high yields under mild conditions. This synthesis is also applied to the reactions of ketones having alpha-protons, and of N-substituted aldimines.

Palladium-Catalyzed Indole, Pyrrole, and Furan Arylation by Aryl Chlorides

PubMed Central

Nadres, Enrico T.; Lazareva, Anna; Daugulis, Olafs

2011-01-01

The palladium-catalyzed direct arylation of indoles, pyrroles, and furans by aryl chlorides has been demonstrated. The method employs a palladium acetate catalyst, 2-(dicyclohexylphosphino)-biphenyl ligand, and an inorganic base. Electron-rich and electron-poor aryl chlorides as well as chloropyridine coupling partners can be used and arylated heterocycles are obtained in moderate to good yields. Optimization of base, ligand, and solvent is required for achieving best results. PMID:21192652

Facially Selective Cu-catalyzed Carbozincation of Cyclopropenes Using Arylzinc Reagents Formed by Sequential I/Mg/Zn exchange

PubMed Central

Tarwade, Vinod; Selvaraj, Ramajeyam; Fox, Joseph M.

2012-01-01

Described is a Cu-catalyzed directed carbozincation of cyclopropenes with organozinc reagents prepared by I/Mg/Zn exchange. This protocol broadens the scope with respect to functional group tolerance and enables use of aryl iodide precursors, rather than purified diorganozinc precursors. Critical to diastereoselectivity of the carbozincation step is the removal of magnesium halide salts after transmetallation with ZnCl2. PMID:23035947

Structural Studies of Geosmin Synthase, a Bifunctional Sesquiterpene Synthase with Alpha-Alpha Domain Architecture that Catalyzes a Unique Cyclization-Fragmentation Reaction Sequence

PubMed Central

Harris, Golda G.; Lombardi, Patrick M.; Pemberton, Travis A.; Matsui, Tsutomu; Weiss, Thomas M.; Cole, Kathryn E.; Köksal, Mustafa; Murphy, Frank V.; Vedula, L. Sangeetha; Chou, Wayne K.W.; Cane, David E.; Christianson, David W.

2015-01-01

Geosmin synthase from Streptomyces coelicolor (ScGS) catalyzes an unusual, metal-dependent terpenoid cyclization and fragmentation reaction sequence. Two distinct active sites are required for catalysis: the N-terminal domain catalyzes the ionization and cyclization of farnesyl diphosphate to form germacradienol and inorganic pyrophosphate (PPi), and the C-terminal domain catalyzes the protonation, cyclization, and fragmentation of germacradienol to form geosmin and acetone through a retro-Prins reaction. A unique αα domain architecture is predicted for ScGS based on amino acid sequence: each domain contains the metal-binding motifs typical of a class I terpenoid cyclase, and each domain requires Mg2+ for catalysis. Here, we report the X-ray crystal structure of the unliganded N-terminal domain of ScGS and the structure of its complex with 3 Mg2+ ions and alendronate. These structures highlight conformational changes required for active site closure and catalysis. Although neither full-length ScGS nor constructs of the C-terminal domain could be crystallized, homology models of the C-terminal domain were constructed based on ~36% sequence identity with the N-terminal domain. Small-angle X-ray scattering experiments yield low resolution molecular envelopes into which the N-terminal domain crystal structure and the C-terminal domain homology model were fit, suggesting possible αα domain architectures as frameworks for bifunctional catalysis. PMID:26598179

Cytochrome P-450 isoforms involved in carboxylic acid ester cleavage of Hantzsch pyridine ester of pranidipine.

PubMed

Kudo, S; Okumura, H; Miyamoto, G; Ishizaki, T

1999-02-01

Cytochrome P-450 (CYP) isoforms responsible for the cleavage of Hantzsch pyridine ester at the 3-position of pranidipine were studied in vitro using cDNA-expressed human CYP enzymes. CYP1A1, 1A2, 2D6, and 3A4 cleaved the ester with a catalytic activity of 5.5, 0. 93, 13.1, and 22.4 nmol/30 min/nmol P-450, respectively. CYP2A6, 2B6, 2C8, 2C9, 2C19, and 2E1 were not involved in the de-esterification. The Km and Vmax values for the de-esterification were 11.8 microM and 0.47 nmol/min/nmol P-450 in the CYP2D6-catalyzed reaction and 8. 7 microM and 0.84 nmol/min/nmol P-450 in the CYP3A4-catalyzed reaction. The intrinsic clearance (Vmax/Km) of the de-esterification by CYP3A4 was 2-fold greater than that by CYP2D6. Quinidine almost completely inhibited the CYP2D6-mediated de-esterification at the concentration of 1 x 10(-6) M. Ketoconazole and troleandomycin inhibited the CYP3A4-mediated reaction in a dose-related manner. The results indicate that although the multiple CYP isoforms can catalyze the de-esterification, CYP3A4 and 2D6 are the major isoforms.

Asymmetric epoxidation of unsaturated ketones catalyzed by heterobimetallic rare earth-lithium complexes bearing phenoxy-functionalized chiral diphenylprolinolate ligand.

PubMed

Qian, Qinqin; Tan, Yufang; Zhao, Bei; Feng, Tao; Shen, Qi; Yao, Yingming

2014-09-05

Four novel heterobimetallic complexes [REL2]{[(THF)3Li]2(μ-Cl)} stabilized by chiral phenoxy-functionalized prolinolate (RE = Yb (1), Y (2), Sm (3), Nd (4), H2L = (S)-2,4-di-tert-butyl-6-[[2-(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol have been synthesized and characterized. These readily available complexes are highly active in catalyzing the epoxidation of α,β-unsaturated ketones, while the enantioselectivity varies according to the ionic radii of the rare earth center. A series of chalcone derivatives were converted to chiral epoxides in 80 → 99% ee at 0 °C using TBHP as the oxidant in the presence of 10 mol % of 1.

A rechargeable hydrogen battery based on Ru catalysis.

PubMed

Hsu, Shih-Fan; Rommel, Susanne; Eversfield, Philipp; Muller, Keven; Klemm, Elias; Thiel, Werner R; Plietker, Bernd

2014-07-01

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H2 battery which is based on the principle of the Ru-catalyzed hydrogenation of CO2 to formic acid (charging process) and the Ru-catalyzed decomposition of formic acid to CO2 and H2 (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure-free conditions (discharging process). Up to five charging-discharging cycles were performed without decrease of storage capacity. The resulting CO2/H2 mixture is free of CO and can be employed directly in fuel-cell technology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Human kidney methoxyflurane and sevoflurane metabolism. Intrarenal fluoride production as a possible mechanism of methoxyflurane nephrotoxicity.

PubMed

Kharasch, E D; Hankins, D C; Thummel, K E

1995-03-01

Methoxyflurane nephrotoxicity is mediated by cytochrome P450-catalyzed metabolism to toxic metabolites. It is historically accepted that one of the metabolites, fluoride, is the nephrotoxin, and that methoxyflurane nephrotoxicity is caused by plasma fluoride concentrations in excess of 50 microM. Sevoflurane also is metabolized to fluoride ion, and plasma concentrations may exceed 50 microM, yet sevoflurane nephrotoxicity has not been observed. It is possible that in situ renal metabolism of methoxyflurane, rather than hepatic metabolism, is a critical event leading to nephrotoxicity. We tested whether there was a metabolic basis for this hypothesis by examining the relative rates of methoxyflurane and sevoflurane defluorination by human kidney microsomes. Microsomes and cytosol were prepared from kidneys of organ donors. Methoxyflurane and sevoflurane metabolism were measured with a fluoride-selective electrode. Human cytochrome P450 isoforms contributing to renal anesthetic metabolism were identified by using isoform-selective inhibitors and by Western blot analysis of renal P450s in conjunction with metabolism by individual P450s expressed from a human hepatic complementary deoxyribonucleic acid library. Sevoflurane and methoxyflurane did undergo defluorination by human kidney microsomes. Fluoride production was dependent on time, reduced nicotinamide adenine dinucleotide phosphate, protein concentration, and anesthetic concentration. In seven human kidneys studied, enzymatic sevoflurane defluorination was minima, whereas methoxyflurane defluorination rates were substantially greater and exhibited large interindividual variability. Kidney cytosol did not catalyze anesthetic defluorination. Chemical inhibitors of the P450 isoforms 2E1, 2A6, and 3A diminished methoxyflurane and sevoflurane defluorination. Complementary deoxyribonucleic acid-expressed P450s 2E1, 2A6, and 3A4 catalyzed methoxyflurane and sevoflurane metabolism, in diminishing order of activity. These three P450s catalyzed the defluorination of methoxyflurane three to ten times faster than they did that of sevoflurane. Expressed P450 2B6 also catalyzed methoxyflurane defluorination, but 2B6 appeared not to contribute to renal microsomal methoxyflurane defluorination because the P450 2B6-selective inhibitor had no effect. Human kidney microsomes metabolize methoxyflurane, and to a much lesser extent sevoflurane, to fluoride ion. P450s 2E1 and/or 2A6 and P450 3A are implicated in the defluorination. If intrarenally generated fluoride or other metabolites are nephrotoxic, then renal metabolism may contribute to methoxyflurane nephrotoxicity. The relative paucity of renal sevoflurane defluorination may explain the absence of clinical sevoflurane nephrotoxicity to date, despite plasma fluoride concentrations that may exceed 50 microM.

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

PubMed

You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

2017-02-03

A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

Synthesis of Donor/Acceptor-Substituted Diazo Compounds in Flow and Their Application in Enantioselective Dirhodium-Catalyzed Cyclopropanation and C-H Functionalization.

PubMed

Rackl, Daniel; Yoo, Chun-Jae; Jones, Christopher W; Davies, Huw M L

2017-06-16

A tandem reaction system has been developed for the preparation of donor/acceptor-substituted diazo compounds in continuous flow coupled to dirhodium-catalyzed C-H functionalization or cyclopropanation. Hydrazones were oxidized in flow by solid-supported N-iodo-p-toluenesulfonamide potassium salt (PS-SO 2 NIK) to generate the diazo compounds, which were then purified by passing through a column of molecular sieves/sodium thiosulfate.

Theoretical prediction and experimental verification on enantioselectivity of haloacid dehalogenase L-DEX YL with chloropropionate

NASA Astrophysics Data System (ADS)

Kondo, Hirotaka; Fujimoto, Kazuhiro J.; Tanaka, Shigenori; Deki, Hiroyuki; Nakamura, Takashi

2015-03-01

L-2-Haloacid dehalogenase (L-DEX YL) is a member of a family of enzymes that decontaminate a variety of environmental pollutants such as L-2-chloropropionate (L-2-CPA). This enzyme specifically catalyzes the hydrolytic dehalogenation of L-2-haloacid to produce D-2-hydroxy acid, and does not catalyze that of D-2-haloacid. Here, using the quantum-mechanical/molecular-mechanical and the fragment molecular orbital calculations, the enzymatic reaction of L-DEX YL to D-2-CPA was compared with that to L-2-CPA. As a result, Tyr12, Leu45 and Phe60 were predicted to affect the enantioselectivity. We then performed the site-directed-mutagenesis experiments and the activity measurement of these mutants, thus finding that the F60Y mutant had the enzymatic activity with D-2-CPA.

Hydrogenation of Carbon Dioxide to Methanol Catalyzed by Iron, Cobalt, and Manganese Cyclopentadienone Complexes: Mechanistic Insights and Computational Design.

PubMed

Ge, Hongyu; Chen, Xiangyang; Yang, Xinzheng

2017-07-03

Density functional theory study of the hydrogenation of carbon dioxide to methanol catalyzed by iron, cobalt, and manganese cyclopentadienone complexes reveals a self-promoted mechanism, which features a methanol- or water-molecule-assisted proton transfer for the cleavage of H 2 . The total free energy barrier of the formation of methanol from CO 2 and H 2 catalyzed by Knölker's iron cyclopentadienone complex, [2,5-(SiMe 3 ) 2 -3,4-(CH 2 ) 4 (η 5 -C 4 COH)]Fe(CO) 2 H, is 26.0 kcal mol -1 in the methanol solvent. We also evaluated the catalytic activities of 8 other experimentally reported iron cyclopentadienone complexes and 37 iron, cobalt, and manganese cyclopentadienone complexes proposed in this study. In general, iron and manganese complexes have relatively higher catalytic activities. Among all calculated complexes, [2,5-(SiMe 3 ) 2 -3,4-CH 3 CHSCH 2 (η 5 -C 4 COH)]Fe(CO) 2 H (1 Fe-Casey-S-CH3 ) is the most active one with a total free energy barrier of 25.1 kcal mol -1 in the methanol solvent. Such a low barrier indicates that 1 Fe-Casey-S-CH3 is a very promising low-cost and high efficiency catalyst for the conversion of CO 2 and H 2 to methanol under mild conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

PubMed

Evans, P Andrew; Negru, Daniela E; Shang, Deju

2015-04-13

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Catalytic Borylation/Dehalogenation Route to o-Fluoro Arylboronates

PubMed Central

2015-01-01

A two-step Ir-catalyzed borylation/Pd-catalyzed dehalogenation sequence allows for the net synthesis of fluoroarenes where the boronic ester is ortho to fluorine. Key elements of this approach include the use of a halogen para to the fluorine to block meta Ir-catalyzed borylation and the chemoselective Pd-catalyzed dehalogenation by KF activated polymethylhydrosiloxane (PMHS). PMID:25418716

A highly efficient synthesis of the FGH ring of micrandilactone A. Application of thioureas as ligands in the Co-catalyzed Pauson-Khand reaction and Pd-catalyzed carbonylative annulation.

PubMed

Tang, Yefeng; Zhang, Yandong; Dai, Mingji; Luo, Tuoping; Deng, Lujiang; Chen, Jiahua; Yang, Zhen

2005-03-03

The functionalized FGH ring system of micrandilactone A was successfully constructed in high selectivity and good yields. The key reactions in our strategy are the Co-thiourea-catalyzed stereoselective, intramolecular Pauson-Khand reaction and Pd-thiourea-catalyzed stereoselective, intramolecular annulation. [structure: see text

Enzymatic synthesis of chiral amino-alcohols by coupling transketolase and transaminase-catalyzed reactions in a cascading continuous-flow microreactor system.

PubMed

Gruber, Pia; Carvalho, Filipe; Marques, Marco P C; O'Sullivan, Brian; Subrizi, Fabiana; Dobrijevic, Dragana; Ward, John; Hailes, Helen C; Fernandes, Pedro; Wohlgemuth, Roland; Baganz, Frank; Szita, Nicolas

2018-03-01

Rapid biocatalytic process development and intensification continues to be challenging with currently available methods. Chiral amino-alcohols are of particular interest as they represent key industrial synthons for the production of complex molecules and optically pure pharmaceuticals. (2S,3R)-2-amino-1,3,4-butanetriol (ABT), a building block for the synthesis of protease inhibitors and detoxifying agents, can be synthesized from simple, non-chiral starting materials, by coupling a transketolase- and a transaminase-catalyzed reaction. However, until today, full conversion has not been shown and, typically, long reaction times are reported, making process modifications and improvement challenging. In this contribution, we present a novel microreactor-based approach based on free enzymes, and we report for the first time full conversion of ABT in a coupled enzyme cascade for both batch and continuous-flow systems. Using the compartmentalization of the reactions afforded by the microreactor cascade, we overcame inhibitory effects, increased the activity per unit volume, and optimized individual reaction conditions. The transketolase-catalyzed reaction was completed in under 10 min with a volumetric activity of 3.25 U ml -1 . Following optimization of the transaminase-catalyzed reaction, a volumetric activity of 10.8 U ml -1 was attained which led to full conversion of the coupled reaction in 2 hr. The presented approach illustrates how continuous-flow microreactors can be applied for the design and optimization of biocatalytic processes. © 2017 The Authors. Biotechnology and Bioengineering Published by Wiley Periodicals, Inc.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

PubMed

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dioxygenases Catalyze O-Demethylation and O,O-Demethylenation with Widespread Roles in Benzylisoquinoline Alkaloid Metabolism in Opium Poppy*

PubMed Central

Farrow, Scott C.; Facchini, Peter J.

2013-01-01

In opium poppy, the antepenultimate and final steps in morphine biosynthesis are catalyzed by the 2-oxoglutarate/Fe(II)-dependent dioxygenases, thebaine 6-O-demethylase (T6ODM) and codeine O-demethylase (CODM). Further investigation into the biochemical functions of CODM and T6ODM revealed extensive and unexpected roles for such enzymes in the metabolism of protopine, benzo[c]phenanthridine, and rhoeadine alkaloids. When assayed with a wide range of benzylisoquinoline alkaloids, CODM, T6ODM, and the functionally unassigned paralog DIOX2, renamed protopine O-dealkylase, showed novel and efficient dealkylation activities, including regio- and substrate-specific O-demethylation and O,O-demethylenation. Enzymes catalyzing O,O-demethylenation, which cleave a methylenedioxy bridge leaving two hydroxyl groups, have previously not been reported in plants. Similar cleavage of methylenedioxy bridges on substituted amphetamines is catalyzed by heme-dependent cytochromes P450 in mammals. Preferred substrates for O,O-demethylenation by CODM and protopine O-dealkylase were protopine alkaloids that serve as intermediates in the biosynthesis of benzo[c]phenanthridine and rhoeadine derivatives. Virus-induced gene silencing used to suppress the abundance of CODM and/or T6ODM transcripts indicated a direct physiological role for these enzymes in the metabolism of protopine alkaloids, and they revealed their indirect involvement in the formation of the antimicrobial benzo[c]phenanthridine sanguinarine and certain rhoeadine alkaloids in opium poppy. PMID:23928311

Dioxygenases catalyze O-demethylation and O,O-demethylenation with widespread roles in benzylisoquinoline alkaloid metabolism in opium poppy.

PubMed

Farrow, Scott C; Facchini, Peter J

2013-10-04

In opium poppy, the antepenultimate and final steps in morphine biosynthesis are catalyzed by the 2-oxoglutarate/Fe(II)-dependent dioxygenases, thebaine 6-O-demethylase (T6ODM) and codeine O-demethylase (CODM). Further investigation into the biochemical functions of CODM and T6ODM revealed extensive and unexpected roles for such enzymes in the metabolism of protopine, benzo[c]phenanthridine, and rhoeadine alkaloids. When assayed with a wide range of benzylisoquinoline alkaloids, CODM, T6ODM, and the functionally unassigned paralog DIOX2, renamed protopine O-dealkylase, showed novel and efficient dealkylation activities, including regio- and substrate-specific O-demethylation and O,O-demethylenation. Enzymes catalyzing O,O-demethylenation, which cleave a methylenedioxy bridge leaving two hydroxyl groups, have previously not been reported in plants. Similar cleavage of methylenedioxy bridges on substituted amphetamines is catalyzed by heme-dependent cytochromes P450 in mammals. Preferred substrates for O,O-demethylenation by CODM and protopine O-dealkylase were protopine alkaloids that serve as intermediates in the biosynthesis of benzo[c]phenanthridine and rhoeadine derivatives. Virus-induced gene silencing used to suppress the abundance of CODM and/or T6ODM transcripts indicated a direct physiological role for these enzymes in the metabolism of protopine alkaloids, and they revealed their indirect involvement in the formation of the antimicrobial benzo[c]phenanthridine sanguinarine and certain rhoeadine alkaloids in opium poppy.

Merging C-H activation and alkene difunctionalization at room temperature: a palladium-catalyzed divergent synthesis of indoles and indolines.

PubMed

Manna, Manash Kumar; Hossian, Asik; Jana, Ranjan

2015-02-06

A palladium-catalyzed 1,2-carboamination through C-H activation at room temperature is reported for the synthesis of 2-arylindoles, and indolines from readily available, inexpensive aryl ureas and vinyl arenes. The reaction initiates with a urea-directed electrophilic ortho palladation, alkene insertion, and β-hydride elimination sequences to provide the Fujiwara-Moritani arylation product. Subsequently, aza-Wacker cyclization, and β-hydride elimination provide the 2-arylindoles in high yields. Intercepting the common σ-alkyl-Pd intermediate, corresponding indolines are also achieved. The indoline formation is attributed to the generation of stabilized, cationic π-benzyl-Pd species to suppress β-hydride elimination.

Cannabidiol-2',6'-dimethyl ether as an effective protector of 15-lipoxygenase-mediated low-density lipoprotein oxidation in vitro.

PubMed

Takeda, Shuso; Hirayama, Akari; Urata, Shino; Mano, Nobutaka; Fukagawa, Keiko; Imamura, Midori; Irii, Ayumi; Kitajima, Satomi; Masuyama, Tomoko; Nomiyama, Mai; Tatei, Sachiko; Tomita, Saari; Kudo, Taichi; Noguchi, Momoko; Yamaguchi, Yasuhiro; Okamoto, Yoshiko; Amamoto, Toshiaki; Fukunishi, Yoshifumi; Watanabe, Kazuhito; Omiecinski, Curtis John; Aramaki, Hironori

2011-01-01

15-Lipoxygenase (15-LOX) is one of the key enzymes responsible for the formation of oxidized low-density lipoprotein (ox-LDL), a major causal factor for atherosclerosis. Both enzymatic (15-LOX) and non-enzymatic (Cu(2+)) mechanisms have been proposed for the production of ox-LDL. We have recently reported that cannabidiol-2',6'-dimethyl ether (CBDD) is a selective and potent inhibitor of 15-LOX-catalyzed linoleic acid oxygenation (Takeda et al., Drug Metab. Dispos., 37, 1733-1737 (2009)). In the LDL, linoleic acid is present as cholesteryl linoleate, the major fatty acid esterified to cholesterol, and is susceptible to oxidative modification by 15-LOX or Cu(2+). In this investigation, we examined the efficacy of CBDD on i) 15-LOX-catalyzed oxygenation of cholesteryl linoleate, and ii) ox-LDL formation catalyzed by 15-LOX versus Cu(2+)-mediated non-enzymatic generation of this important mediator. The results obtained demonstrate that CBDD is a potent and selective inhibitor of ox-LDL formation generated by the 15-LOX pathway. These studies establish CBDD as both an important experimental tool for characterizing 15-LOX-mediated ox-LDL formation, and as a potentially useful therapeutic agent for treatment of atherosclerosis.

Cannabidiol-2′,6′-dimethyl Ether as an Effective Protector of 15-Lipoxygenase-Mediated Low-Density Lipoprotein Oxidation in Vitro

PubMed Central

Takeda, Shuso; Hirayama, Akari; Urata, Shino; Mano, Nobutaka; Fukagawa, Keiko; Imamura, Midori; Irii, Ayumi; Kitajima, Satomi; Masuyama, Tomoko; Nomiyama, Mai; Tatei, Sachiko; Tomita, Saari; Kudo, Taichi; Noguchi, Momoko; Yamaguchi, Yasuhiro; Okamoto, Yoshiko; Amamoto, Toshiaki; Fukunishi, Yoshifumi; Watanabe, Kazuhito; Omiecinski, Curtis John; Aramaki, Hironori

2014-01-01

15-Lipoxygenase (15-LOX) is one of the key enzymes responsible for the formation of oxidized low-density lipoprotein (ox-LDL), a major causal factor for atherosclerosis. Both enzymatic (15-LOX) and non-enzymatic (Cu2+) mechanisms have been proposed for the production of ox-LDL. We have recently reported that cannabidiol-2′,6′-dimethyl ether (CBDD) is a selective and potent inhibitor of 15-LOX-catalyzed linoleic acid oxygenation (Takeda et al., Drug Metab. Dispos., 37, 1733–1737 (2009)). In the LDL, linoleic acid is present as cholesteryl linoleate, the major fatty acid esterified to cholesterol, and is susceptible to oxidative modification by 15-LOX or Cu2+. In this investigation, we examined the efficacy of CBDD on i) 15-LOX-catalyzed oxygenation of cholesteryl linoleate, and ii) ox-LDL formation catalyzed by 15-LOX versus Cu2+-mediated non-enzymatic generation of this important mediator. The results obtained demonstrate that CBDD is a potent and selective inhibitor of ox-LDL formation generated by the 15-LOX pathway. These studies establish CBDD as both an important experimental tool for characterizing 15-LOX-mediated ox-LDL formation, and as a potentially useful therapeutic agent for treatment of atherosclerosis. PMID:21804214

Copper-Based Metal-Organic Framework Nanoparticles with Peroxidase-Like Activity for Sensitive Colorimetric Detection of Staphylococcus aureus.

PubMed

Wang, Shuqin; Deng, Wenfang; Yang, Lu; Tan, Yueming; Xie, Qingji; Yao, Shouzhuo

2017-07-26

Cu-MOF nanoparticles with an average diameter of 550 nm were synthesized from 2-aminoterephthalic acid and Cu(NO 3 ) 2 by a mixed solvothermal method. The Cu-MOF nanoparticles can show peroxidase-like activity that can catalyze 3,3',5,5'-tetramethylbenzidine to produce a yellow chromogenic reaction in the presence of H 2 O 2 . The presence of abundant amine groups on the surfaces of Cu-MOF nanoparticles enables facile modification of Staphylococcus aureus (S. aureus) aptamer on Cu-MOF nanoparticles. By combining Cu-MOF-catalyzed chromogenic reaction with aptamer recognition and magnetic separation, a simple, sensitive, and selective colorimetric method for the detection of S. aureus was developed.

Rhodium(I)-catalyzed cyclization of allenynes with a carbonyl group through unusual insertion of a C-O bond into a rhodacycle intermediate.

PubMed

Oonishi, Yoshihiro; Yokoe, Takayuki; Hosotani, Akihito; Sato, Yoshihiro

2014-01-20

Rhodium(I)-catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a CO bond into the C(sp(2) )-rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8-oxabicyclo[3.2.1]octane skeleton, while β-hydride elimination from the same intermediate gives products that contain fused five- and seven-membered rings in high yields. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of (E)-2-Styrylchromones and Flavones by Base-Catalyzed Cyclodehydration of the Appropriate β-Diketones Using Water as Solvent.

PubMed

Pinto, Joana; Silva, Vera L M; Silva, Ana M G; Silva, Artur M S

2015-06-22

A low cost, safe, clean and environmentally benign base-catalyzed cyclodehydration of appropriate β-diketones affording (E)-2-styrylchromones and flavones in good yields is disclosed. Water was used as solvent and the reactions were heated using classical and microwave heating methods, under open and closed vessel conditions. β-Diketones having electron-donating and withdrawing substituents were used to evaluate the reaction scope. The reaction products were isolated in high purity by simple filtration and recrystallization from ethanol, when using 800 mg of the starting diketone under classical reflux heating conditions.

Generation of C3- and C2-deuterated L-lactic acid by human erythrocytes exposed to D-[1-13C]glucose, D-[2-13C]glucose and D-[6-13C]glucose in the presence of D2O.

PubMed

Malaisse, W J; Biesemans, M; Willem, R

1994-05-01

1. The generation of C2- and C3-deuterated L-lactate was monitored by 13C NMR in human erythrocytes exposed to D-[1-13C]glucose, D-[2-13C]glucose or D-[6-13C]glucose and incubated in a medium prepared in D2O. 2. The results suggested that the deuteration of the C1 of D-fructose 6-phosphate in the phosphoglucoisomerase reaction, the deuteration of the C1 of D-glyceraldehyde-3-phosphate in the sequence of reactions catalyzed by triose phosphate isomerase and aldolase and the deuteration of the C3 of pyruvate in the reaction catalyzed by pyruvate kinase were all lower than expected from equilibration with D2O. 3. Moreover, about 40% of the molecules of pyruvate generated by glycolysis apparently underwent deuteration on their C3 during interconversion of the 2-keto acid and L-alanine in the reaction catalyzed by glutamate-pyruvate transaminase. 4. The occurrence of the latter process was also documented in cells exposed to exogenous [3-13C]pyruvate. 5. This methodological approach is proposed to provide a new tool to assess in intact cells the extent of back-and-forth interconversion of selected metabolic intermediates.

Prediction of Stereochemistry using Q2MM

PubMed Central

2016-01-01

Conspectus The standard method of screening ligands for selectivity in asymmetric, transition metal-catalyzed reactions requires experimental testing of hundreds of ligands from ligand libraries. This “trial and error” process is costly in terms of time as well as resources and, in general, is scientifically and intellectually unsatisfying as it reveals little about the underlying mechanism behind the selectivity. The accurate computational prediction of stereoselectivity in enantioselective catalysis requires adequate conformational sampling of the selectivity-determining transition state but has to be fast enough to compete with experimental screening techniques to be useful for the synthetic chemist. Although electronic structure calculations are accurate and general, they are too slow to allow for sampling or fast screening of ligand libraries. The combined requirements can be fulfilled by using appropriately fitted transition state force fields (TSFFs) that represent the transition state as a minimum and allow fast conformational sampling using Monte Carlo. Quantum-guided molecular mechanics (Q2MM) is an automated force field parametrization method that generates accurate, reaction-specific TSFFs by fitting the functional form of an arbitrary force field using only electronic structure calculations by minimization of an objective function. A key feature that distinguishes the Q2MM method from many other automated parametrization procedures is the use of the Hessian matrix in addition to geometric parameters and relative energies. This alleviates the known problems of overfitting of TSFFs. After validation of the TSFF by comparison to electronic structure results for a test set and available experimental data, the stereoselectivity of a reaction can be calculated by summation over the Boltzman-averaged relative energies of the conformations leading to the different stereoisomers. The Q2MM method has been applied successfully to perform virtual ligand screens on a range of transition metal-catalyzed reactions that are important from both an industrial and an academic perspective. In this Account, we provide an overview of the continued improvement of the prediction of stereochemistry using Q2MM-derived TSFFs using four examples from different stages of development: (i) Pd-catalyzed allylation, (ii) OsO4-catalyzed asymmetric dihydroxylation (AD) of alkenes, (iii) Rh-catalyzed hydrogenation of enamides, and (iv) Ru-catalyzed hydrogenation of ketones. In the current form, correlation coefficients of 0.8–0.9 between calculated and experimental ee values are typical for a wide range of substrate–ligand combinations, and suitable ligands can be predicted for a given substrate with ∼80% accuracy. Although the generation of a TSFF requires an initial effort and will therefore be most useful for widely used reactions that require frequent screening campaigns, the method allows for a rapid virtual screen of large ligand libraries to focus experimental efforts on the most promising substrate–ligand combinations. PMID:27064579

Evaluation of hydrogen isotope exchange methodology on adsorbents for tritium removal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morgan, G.A.; Xin Xiao, S.

2015-03-15

The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H{sub 2} (when flowed through the molecular sieves) will exchange with the adsorbed water, D{sub 2}O, leaving H{sub 2}O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminatedmore » water (T{sub 2}O, HTO, and DTO) using D{sub 2} (or H{sub 2}). (authors)« less

Regioselective Ni-Catalyzed Carboxylation of Allylic and Propargylic Alcohols with Carbon Dioxide.

PubMed

Chen, Yue-Gang; Shuai, Bin; Ma, Cong; Zhang, Xiu-Jie; Fang, Ping; Mei, Tian-Sheng

2017-06-02

An efficient Ni-catalyzed reductive carboxylation of allylic alcohols with CO 2 has been successfully developed, providing linear β,γ-unsaturated carboxylic acids as the sole regioisomer with generally high E/Z stereoselectivity. In addition, the carboxylic acids can be generated from propargylic alcohols via hydrogenation to give allylic alcohol intermediates, followed by carboxylation. A preliminary mechanistic investigation suggests that the hydrogenation step is made possible by a Ni hydride intermediate produced by a hydrogen atom transfer from water.

The applicability of the catalytic wet-oxidation to CELSS

NASA Technical Reports Server (NTRS)

Takahashi, Y.; Nitta, K.; Ohya, H.; Oguchi, M.

1987-01-01

The wet oxidation catalysis of Au, Pd, Pt, Rh or Ru on a ceramic honeycomb carrier was traced in detail by 16 to 20 repetitive batch tests each. As a result, Pt or Pd on a honeycomb carrier was shown to catalyze complete nitrogen gasification as N2. Though the catalysts which realize both complete nitrogen gasification and complete oxidation could not be found, the Ru+Rh catalyst was found to be most promising. Ru honeycomb catalyzed both nitrification and nitrogen gasification.

Regio- and enantioselective synthesis of N-substituted pyrazoles by rhodium-catalyzed asymmetric addition to allenes.

PubMed

Haydl, Alexander M; Xu, Kun; Breit, Bernhard

2015-06-08

The rhodium-catalyzed asymmetric N-selective coupling of pyrazole derivatives with terminal allenes gives access to enantioenriched secondary and tertiary allylic pyrazoles, which can be employed for the synthesis of medicinally important targets. The reaction tolerates a large variety of functional groups and labelling experiments gave insights into the reaction mechanism. This new methodology was further applied in a highly efficient synthesis of JAK 1/2 inhibitor (R)-ruxolitinib. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Histidine-functionalized water-soluble nanoparticles for biomimetic nucleophilic/general-base catalysis under acidic conditions.

PubMed

Chadha, Geetika; Zhao, Yan

2013-10-21

Cross-linking the micelles of 4-dodecyloxybenzyltripropargylammonium bromide by 1,4-diazidobutane-2,3-diol in the presence of azide-functionalized imidazole derivatives yielded surface-cross-linked micelles (SCMs) with imidazole groups on the surface. The resulting water-soluble nanoparticles were found, by fluorescence spectroscopy, to contain hydrophobic binding sites. The imidazole groups promoted the photo-deprotonation of 2-naphthol at pH 6 and catalyzed the hydrolysis of p-nitrophenylacetate (PNPA) in aqueous solution at pH ≥ 4. Although the overall hydrolysis rate slowed down with decreasing solution pH, the catalytic effect of the imidazole became stronger because the reactions catalyzed by unfunctionalized SCMs slowed down much more. The unusual ability of the imidazole–SCMs to catalyze the hydrolysis of PNPA under acidic conditions was attributed to the local hydrophobicity and the positive nature of the SCMs.

Facile conversion of a coordinated nitro group into an aqua group: acid-induced nitro-to-nitro rearrangement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackson, W.G.

1987-11-18

The nitro complex (NH/sub 3/)/sub 5/CoNO/sub 2//sup 2 +/ reacts rapidly and completely with neat anhydrous trifluoromethanesulfonic acid to generate the aqua species (NH/sub 3/)/sub 5/CoOH/sub 2//sup 3 +/. Oxygen-17 NMR results show that the oxygen in the bound water is derived from the original nitro group. A mechanism involving acid-catalyzed nitrogen-to-oxygen nitrite rearrangement is considered. The relationship between the mechanisms for oxygen scrambling and acid-catalyzed loss of NO/sup +/ from the nitrito linkage isomer is discussed, together with the mechanism for the present reaction. 20 references, 1 figure.

Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH.

PubMed

Zhang, Jing; Zhang, Ying; Wang, Hui; Guan, Xiaohong

2014-07-01

Ru(III) was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru(III) could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru(III) catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru(III), respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru(III) catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant (ktapp) decreased from 643.20 to 2.67 (mol/L)⁻¹sec⁻¹ with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru(III), as an electron shuttle, was oxidized by permanganate to Ru(VI) and Ru(VII), which acted the co-oxidants for decomposition of aniline. Although Ru(III) could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru(III) into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru(III) toward permanganate oxidation in our future study. Copyright © 2014. Published by Elsevier B.V.

Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles

2011-01-01

This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

DOE PAGES

Shrestha, Bijay; Basnet, Prakash; Dhungana, Roshan K.; ...

2017-07-24

We disclose a strategy for Ni-catalyzed regioselective dicarbofunctionalization of olefins in styrene derivatives by intercepting Heck C(sp 3)-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometallation, and stabilizing the Heck C(sp 3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely-substituted 1,1,2-riarylethyl products that occur as structural motifs in various natural products.

Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

PubMed

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

EPR probes with well-defined, long distances between two or three unpaired electrons

PubMed

Godt; Franzen; Veit; Enkelmann; Pannier; Jeschke

2000-11-03

The synthesis of rod- and star-shaped compounds carrying two or three spin labels as end groups is described. The unpaired electrons are 2.8-5.1 nm apart from each other. The shape-persistent scaffolds were obtained through Pd-Cu-catalyzed alkynyl-aryl coupling and Pd-Cu-catalyzed alkyne dimerization in the presence of oxygen using p-phenyleneethynylene as the basic shape-persistent building block. The spin label 1-oxyl-2,2,5,5-tetramethylpyrroline-3-carboxylic acid (4) was attached through esterification of the terminal phenolic OH groups of the scaffold.

Solvent effect on copper-catalyzed azide-alkyne cycloaddition (CuAAC): synthesis of novel triazolyl substituted quinolines as potential anticancer agents.

PubMed

Ellanki, Amarender Reddy; Islam, Aminul; Rama, Veera Swamy; Pulipati, Ranga Prasad; Rambabu, D; Krishna, G Rama; Reddy, C Malla; Mukkanti, K; Vanaja, G R; Kalle, Arunasree M; Kumar, K Shiva; Pal, Manojit

2012-05-15

A regioselective route to novel mono triazolyl substituted quinolines has been developed via copper-catalyzed azide-alkyne cycloaddition (CuAAC) of 2,4-diazidoquinoline with terminal alkynes in DMF. The reaction provided bis triazolyl substituted quinolines when performed in water in the presence of Et(3)N. A number of the compounds synthesized showed promising anti-proliferative properties when tested in vitro especially against breast cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sonochemical enzyme-catalyzed regioselective acylation of flavonoid glycosides.

PubMed

Ziaullah; Rupasinghe, H P Vasantha

2016-04-01

This work compares a highly efficient and alternative method of sonication-assisted lipase catalyzed acylation of quercetin-3-O-glucoside and phloretin-2'-glucoside, using Candida antarctica lipase B (Novozyme 435(®)), with a range of fatty acids. In this study, sonication-assisted irradiation coupled with stirring has been found to be more efficient and economical than conventional reaction conditions. Sonication-assisted acylation accelerated the reactions and reduced the time required by 4-5 folds. Copyright © 2016 Elsevier Inc. All rights reserved.

Dinuclear Zinc-Prophenol-Catalyzed Enantioselective α-Hydroxyacetate Aldol Reaction with Activated Ester Equivalents

PubMed Central

Trost, Barry M.; Michaelis, David J.; Truica, Mihai I.

2013-01-01

An enantioselective α-hydroxyacetate aldol reaction that employs N-acetyl pyrroles as activated ester equivalents and generates syn 1,2-diols in good yield and diastereoselectivity is reported. This dinuclear zinc Prophenol-catalyzed transformation proceeds with high enantioselectivity with a wide variety of substrates including aryl, alyl, and alkenyl aldehydes. The resulting α,β-dihydroxy activated esters are versatile intermediates for the synthesis of a variety of carboxylic acid derivatives including amides, esters, and unsymmetrical ketones. PMID:23947595

Effect of lipase immobilization on resolution of (R, S)-2-octanol in nonaqueous media using modified ultrastable-Y molecular sieve as support.

PubMed

Dai, Dazhang; Xia, Liming

2006-07-01

The lipase from Penicillium expansum PED-03 (PEL) was immobilized onto modified ultrastable-Y (USY) molecular sieve and the resolution of (R, S)- 2-octanol was carried out in a bioreactor in nonaqueous media by the immobilized lipase. It was found that the conversion rate, enantiomeric excess (ee) value, and enantioselectivity (E) value of the resolution catalyzed by PEL immobilized on modified USY molecular sieve were much higher than those of the reaction catalyzed by free PEL and PEL immobilized on other supports. Immobilized on modified USY molecular sieve, the PEL exhibited obvious activity within a wider pH range and at a much higher temperature and showed a markedly enhanced stability against thermal inactivation, by which the suitable pH of the buffer used for immobilization could be "memorized." The conversion rate of the reaction catalyzed by PEL immobilized on modified USY molecular sieve reached 48.84%, with excellent enantioselectivity (average E value of eight batches >460) in nonaqueous media at "memorial" pH 9.5, 50 degrees C for 24 h, demonstrating a good application potential in the production of optically pure (R, S)-2-octanol.

Long-term chemiluminescence signal is produced in the course of luminol oxidation catalyzed by enhancer-independent peroxidase purified from Jatropha curcas leaves.

PubMed

Duan, Peipei; Cai, Feng; Luo, Yongting; Chen, Yangxi; Zou, Shujuan

2015-09-01

Isoenzyme c of horseradish peroxidase (HRP-C) is widely used in enzyme immunoassay combined with chemiluminescence (CL) detection. For this application, HRP-C activity measurement is usually based on luminol oxidation in the presence of hydrogen peroxide (H2O2). However, this catalysis reaction was enhancer dependent. In this study, we demonstrated that Jatropha curcas peroxidase (JcGP1) showed high efficiency in catalyzing luminol oxidation in the presence of H2O2. Compared with HRP-C, the JcGP1-induced reaction was enhancer independent, which made the enzyme-linked immunosorbent assay (ELISA) simpler. In addition, the JcGP1 catalyzed reaction showed a long-term stable CL signal. We optimized the conditions for JcGP1 catalysis and determined the favorable conditions as follows: 50 mM Tris buffer (pH 8.2) containing 10 mM H2 O2, 14 mM luminol and 0.75 M NaCl. The optimum catalysis temperature was 30°C. The detection limit of JcGP1 under optimum condition was 0.2 pM. Long-term stable CL signal combined with enhancer-independent property indicated that JcGP1 might be a valuable candidate peroxidase for clinical diagnosis and enzyme immunoassay with CL detection. Copyright © 2014 John Wiley & Sons, Ltd.

Gold(III) chloride catalyzed synthesis of chiral substituted 3-formyl furans from carbohydrates: application in the synthesis of 1,5-dicarbonyl derivatives and furo[3,2-c]pyridine.

PubMed

Mal, Kanchan; Sharma, Abhinandan; Das, Indrajit

2014-09-08

This report describes a gold(III)-catalyzed efficient general route to densely substituted chiral 3-formyl furans under extremely mild conditions from suitably protected 5-(1-alkynyl)-2,3-dihydropyran-4-one using H2 O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne-gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti-endo-dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2 O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2 O to result in a substituted furo[3,2-c]pyran derivative, as anticipated. The similar furo[3,2-c]pyran skeleton with a hybrid carbohydrate-furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3-formyl furan. The corresponding protected 5-(1-alkynyl)-2,3-dihydropyran-4-one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3-formyl furan derivatives, a TiBr4 -catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5-dicarbonyl compounds, which on treatment with NH4 OAc in slightly acidic conditions afforded substituted furo[3,2-c]pyridine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trapping of intermediates with substrate analog HBOCoA in the polymerizations catalyzed by class III polyhydroxybutyrate (PHB) synthase from Allochromatium vinosum.

PubMed

Chen, Chao; Cao, Ruikai; Shrestha, Ruben; Ward, Christina; Katz, Benjamin B; Fischer, Christopher J; Tomich, John M; Li, Ping

2015-05-15

Polyhydroxybutyrate (PHB) synthases (PhaCs) catalyze the formation of biodegradable PHB polymers that are considered as an ideal alternative to petroleum-based plastics. To provide strong evidence for the preferred mechanistic model involving covalent and noncovalent intermediates, a substrate analog HBOCoA was synthesized chemoenzymatically. Substitution of sulfur in the native substrate HBCoA with an oxygen in HBOCoA enabled detection of (HB)nOCoA (n = 2-6) intermediates when the polymerization was catalyzed by wild-type (wt-)PhaECAv at 5.84 h(-1). This extremely slow rate is due to thermodynamically unfavorable steps that involve the formation of enzyme-bound PHB species (thioesters) from corresponding CoA oxoesters. Synthesized standards (HB)nOCoA (n = 2-3) were found to undergo both reacylation and hydrolysis catalyzed by the synthase. Distribution of the hydrolysis products highlights the importance of the penultimate ester group as previously suggested. Importantly, the reaction between primed synthase [(3)H]-sT-PhaECAv and HBOCoA yielded [(3)H]-sTet-O-CoA at a rate constant faster than 17.4 s(-1), which represents the first example that a substrate analog undergoes PHB chain elongation at a rate close to that of the native substrate (65.0 s(-1)). Therefore, for the first time with a wt-synthase, strong evidence was obtained to support our favored PHB chain elongation model.

Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid.

PubMed

Huang, Yong; Song, Liangliang; Gong, Lei; Meggers, Eric

2015-12-01

A bis-cyclometalated chiral-at-metal rhodium complex catalyzes the Diels-Alder reaction between N-Boc-protected 3-vinylindoles (Boc = tert-butyloxycarbonyl) and β-carboxylic ester-substituted α,β-unsaturated 2-acyl imidazoles with good-to-excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92-99% ee) under optimized conditions. The rhodium catalyst serves as a chiral Lewis acid to activate the 2-acyl imidazole dienophile by two-point binding and overrules the preferred regioselectivity of the uncatalyzed reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic isotope effects reveal early transition state of protein lysine methyltransferase SET8

PubMed Central

Linscott, Joshua A.; Kapilashrami, Kanishk; Wang, Zhen; Senevirathne, Chamara; Bothwell, Ian R.; Blum, Gil; Luo, Minkui

2016-01-01

Protein lysine methyltransferases (PKMTs) catalyze the methylation of protein substrates, and their dysregulation has been linked to many diseases, including cancer. Accumulated evidence suggests that the reaction path of PKMT-catalyzed methylation consists of the formation of a cofactor(cosubstrate)–PKMT–substrate complex, lysine deprotonation through dynamic water channels, and a nucleophilic substitution (SN2) transition state for transmethylation. However, the molecular characters of the proposed process remain to be elucidated experimentally. Here we developed a matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) method and corresponding mathematic matrix to determine precisely the ratios of isotopically methylated peptides. This approach may be generally applicable for examining the kinetic isotope effects (KIEs) of posttranslational modifying enzymes. Protein lysine methyltransferase SET8 is the sole PKMT to monomethylate histone 4 lysine 20 (H4K20) and its function has been implicated in normal cell cycle progression and cancer metastasis. We therefore implemented the MS-based method to measure KIEs and binding isotope effects (BIEs) of the cofactor S-adenosyl-l-methionine (SAM) for SET8-catalyzed H4K20 monomethylation. A primary intrinsic 13C KIE of 1.04, an inverse intrinsic α-secondary CD3 KIE of 0.90, and a small but statistically significant inverse CD3 BIE of 0.96, in combination with computational modeling, revealed that SET8-catalyzed methylation proceeds through an early, asymmetrical SN2 transition state with the C-N and C-S distances of 2.35–2.40 Å and 2.00–2.05 Å, respectively. This transition state is further supported by the KIEs, BIEs, and steady-state kinetics with the SAM analog Se-adenosyl-l-selenomethionine (SeAM) as a cofactor surrogate. The distinct transition states between protein methyltransferases present the opportunity to design selective transition-state analog inhibitors. PMID:27940912

Degradation of the metal-cyano complex tetracyanonickelate (II) by Fusarium oxysporum N-10.

PubMed

Yanase, H; Sakamoto, A; Okamoto, K; Kita, K; Sato, Y

2000-03-01

A fungus with the ability to utilize a metalcyano compound, tetracyanonickelate (II) ¿K2[Ni (CN)4]; TCN¿, as its sole source of nitrogen was isolated from soil and identified as Fusarium oxysporum N-10. Both intact mycelia and cell-free extract of the strain catalyzed hydrolysis of TCN to formate and ammonia and produced formamide as an intermediate, thereby indicating that a hydratase and an amidase sequentially participated in the degradation of TCN. The enzyme catalyzing the hydration of TCN was purified approximately ten-fold from the cell-free extract of strain N-10 with a yield of 29%. The molecular mass of the active enzyme was estimated to be 160 kDa. The enzyme appears to exist as a homotetramer, each subunit having a molecular mass of 40 kDa. The enzyme also catalyzed the hydration of KCN, with a cyanide-hydrating activity 2 x 10(4) times greater than for TCN. The kinetic parameters for TCN and KCN indicated that hydratase isolated from F. oxysporum was a cyanide hydratase able to utilize a broad range of cyano compounds and nitriles as substrates.

Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, to Generate Carbon–Boron Bonds

PubMed Central

Dudnik, Alexander S.

2012-01-01

Through the use of a catalyst formed in situ from NiBr2•diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as −10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition. PMID:22668072

Palladium-catalyzed cyclization reactions of 2-vinylthiiranes with heterocumulenes. Regioselective and enantioselective formation of thiazolidine, oxathiolane, and dithiolane derivatives.

PubMed

Larksarp, C; Sellier, O; Alper, H

2001-05-18

The first palladium-catalyzed ring-expansion reaction of 2-vinylthiiranes with heterocumulenes to form sulfur-containing five-membered-ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of bidendate phosphine ligand (dppp, BINAP), at 50-80 degrees C, in THF. The reaction of 2-vinylthiiranes with carbodiimides, isocyanates, and ketenimines affords 1,3-thiazolidine derivatives, whereas the reaction with diphenylketene or isothiocyanates results in the formation of 1,3-oxathiolane or 1,3-dithiolane compounds in good to excellent isolated yields and in up to 78% ee.

Enzyme-free detection of sequence-specific microRNAs based on nanoparticle-assisted signal amplification strategy.

PubMed

Li, Ru-Dong; Wang, Qian; Yin, Bin-Cheng; Ye, Bang-Ce

2016-03-15

Developing direct and convenient methods for microRNAs (miRNAs) analysis is of great significance in understanding biological functions of miRNAs, and early diagnosis of cancers. We have developed a rapid, enzyme-free method for miRNA detection based on nanoparticle-assisted signal amplification coupling fluorescent metal nanoclusters as signal output. The proposed method involves two processes: target miRNA-mediated nanoparticle capture, which consists of magnetic microparticle (MMP) probe and CuO nanoparticle (NP) probe, and nanoparticle-mediated amplification for signal generation, which consists of fluorescent DNA-Cu/Ag nanocluster (NC) and 3-mercaptopropionic acid (MPA). In the presence of target miRNA, MMP probe and NP probe sandwich-capture the target miRNA via their respective complementary sequence. The resultant sandwich complex (MMP probe-miRNA-CuO NP probe) is separated using a magnetic field and further dissolved by acidolysis to turn CuO NP into a great amount of copper (II) ions (Cu(2+)). Cu(2+) could disrupt the interactions between thiol moiety of MPA and the fluorescent Cu/Ag NCs by preferentially reacting with MPA to form a disulfide compound as intermediate. By this way, the fluorescence emission of the DNA-Cu/Ag NCs in the presence of MPA increases upon the increasing concentration of Cu(2+), which is directly proportional to the amount of target miRNA. The proposed method allows quantitative detection of a liver-specific miR-221-5p in the range of 5 pM to 1000 pM with a detection limit of ~0.73 pM, and shows a good ability to discriminate single-base difference. Moreover, the detection assay can be applied to detect miRNA in cancerous cell lysates in excellent agreement with that from a commercial miRNA detection kit. Copyright © 2015 Elsevier B.V. All rights reserved.

Rhodium-catalyzed Intra- and Intermolecular [5+2] Cycloaddition of 3-Acyloxy-1,4-enyne and Alkyne with Concomitant 1,2-Acyloxy Migration

PubMed Central

Shu, Xing-Zhong; Li, Xiaoxun; Shu, Dongxu; Huang, Suyu; Schienebeck, Casi M.; Zhou, Xin; Robichaux, Patrick J.; Tang, Weiping

2012-01-01

A new type of rhodium-catalyzed [5+2] cycloaddition was developed for the synthesis of seven-membered rings with diverse functionalities. The ring formation was accompanied by a 1,2-acyloxy migration event. The 5- and 2-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes (ACEs) and alkynes respectively. Cationic rhodium (I) catalysts worked most efficiently for the intramolecular cycloaddition, while only neutral rhodium (I) complexes could facilitate the intermolecular reaction. In both cases, electron-poor phosphite or phosphine ligands often improved the efficiency of the cycloadditions. The scope of ACEs and alkynes was investigated in both intra- and intermolecular reactions. The resulting seven-membered ring products have three double bonds that could be selectively functionalized. PMID:22364320

Asymmetric Additions to Dienes Catalyzed by a Dithiophosphoric Acid

PubMed Central

Shapiro, Nathan D.; Rauniyar, Vivek; Hamilton, Gregory L.; Wu, Jeffrey; Toste, F. Dean

2011-01-01

Chiral Brønsted acids have become an invaluable tool for achieving a variety of asymmetric chemical transformations under catalytic conditions while avoiding the use of toxic and expensive metals1–8. While the catalysts developed so far are remarkably effective at activating polarized functional groups, chemists have not yet been able to use organic Brønsted acids to catalyze highly enantioselective transformations of unactivated carbon-carbon multiple bonds. This deficiency persists despite the fact that racemic acid-catalyzed “Markovnikov” additions to olefins are a well-established part of the chemist’s toolbox. Here we show that chiral dithiophosphoric acids catalyze the intramolecular hydroamination and hydroarylation of dienes and allenes to generate heterocyclic products in exceptional yield and enantiomeric excess. To help rationalize the unique success of this catalytic system, we present a mechanistic hypothesis that involves the addition of the acid catalyst to the diene followed by SN2′ displacement of the resulting dithiophosphate intermediate. Mass spectrometry and deuterium labelling studies are presented in support of the proposed mechanism. The catalysts and concepts revealed in this study should prove applicable to other asymmetric functionalizations of unsaturated systems. PMID:21307938

The structure of dimethylallyl tryptophan synthase reveals a common architecture of aromatic prenyltransferases in fungi and bacteria

PubMed Central

Metzger, Ute; Schall, Christoph; Zocher, Georg; Unsöld, Inge; Stec, Edyta; Li, Shu-Ming; Heide, Lutz; Stehle, Thilo

2009-01-01

Ergot alkaloids are toxins and important pharmaceuticals that are produced biotechnologically on an industrial scale. The first committed step of ergot alkaloid biosynthesis is catalyzed by dimethylallyl tryptophan synthase (DMATS; EC 2.5.1.34). Orthologs of DMATS are found in many fungal genomes. We report here the x-ray structure of DMATS, determined at a resolution of 1.76 Å. A complex of DMATS from Aspergillus fumigatus with its aromatic substrate L-tryptophan and with an analogue of its isoprenoid substrate dimethylallyl diphosphate reveals the structural basis of this enzyme-catalyzed Friedel-Crafts reaction, which shows strict regiospecificity for position 4 of the indole nucleus of tryptophan as well as unusual independence of the presence of Mg2+ ions. The 3D structure of DMATS belongs to a rare β/α barrel fold, called prenyltransferase barrel, that was recently discovered in a small group of bacterial enzymes with no sequence similarity to DMATS. These bacterial enzymes catalyze the prenylation of aromatic substrates in the biosynthesis of secondary metabolites (i.e., a reaction similar to that of DMATS). PMID:19706516

Development of a second generation palladium-catalyzed cycloalkenylation and its application to bioactive natural product synthesis.

PubMed

Toyota, Masahiro

2013-07-01

A novel palladium-catalyzed intramolecular oxidative alkylation of unactivated olefins is described. This protocol was devised to solve one of the drawbacks of the original palladium-catalyzed cycloalkenylation that we developed. We call this new procedure the 'second generation palladium-catalyzed cycloalkenylation'. This protocol has been applied to the total syntheses of cis-195A, trans-195A, boonein, scholareins A, C, D, and alpha-skytanthine.

Can Chlorine Anion Catalyze the Reaction fo HOCl with HCl?

NASA Technical Reports Server (NTRS)

Richardson, S. L.; Francisco, J. S.; Mebel, A. M.; Morokuma, K.

1997-01-01

The reaction of HOCl + HCl -> Cl2 + H20 in the presence of Cl has been studied using ab initio methods. This reaction has been shown to have a high activation barrier of 46.5 kcal/mol. The chlorine anion, Cl- is found to catalyze the reaction, viz. two mechanisms. The first involves Cl- interacting through the concerted four-center transition state of the neutral reaction. The other mechanism involves the formation of a HCl-HOCl-Cl- intermediate which dissociates into Cl2 + Cl- + H20. The steps are found to have no barriers. The overall exothermicity is 15.5 kcal/mol.

Theoretical investigation for the reaction of NO 2 with CO catalyzed by Sc +

NASA Astrophysics Data System (ADS)

Wang, Yong-Cheng; Zhang, Jian-Hui; Geng, Zhi-Yuan; Chen, Dong-Ping; Liu, Ze-Yu; Yang, Xiao-Yan

2007-09-01

The mechanism of the reaction NO(2A)+CO(1∑+)→NO(2∏)+CO(1∑g+) catalyzed by Sc + has been investigated by means of UB3LYP/6-311+G(2d) level. Our calculated results strongly indicate that both the reactions NO 2( 2A 1) + Sc +(X 3D) → NO( 2∏) + ScO +(X 1∑ +) and ScO(X1∑+)+CO(1∑+)→Sc(XD)+CO(1∑g+) are spin-forbidden reactions. The crossing points (CPs) that are involved and the possible spin inversion processes are discussed using the intrinsic reaction coordinate (IRC) approach. On the basis of Hammond postulate, they are typical 'two-state reactivity' (TSR) reactions. And the O-atom affinities (OA) testified that the argumentation is thermodynamically allowed.

Synthesis of 3-iodoindoles by the Pd/Cu-catalyzed coupling of N,N-dialkyl-2-iodoanilines and terminal acetylenes, followed by electrophilic cyclization.

PubMed

Yue, Dawei; Yao, Tuanli; Larock, Richard C

2006-01-06

[reaction: see text] 3-Iodoindoles have been prepared in excellent yields by coupling terminal acetylenes with N,N-dialkyl-o-iodoanilines in the presence of a Pd/Cu catalyst, followed by an electrophilic cyclization of the resulting N,N-dialkyl-o-(1-alkynyl)anilines using I2 in CH2Cl2. Aryl-, vinylic-, alkyl-, and silyl-substituted terminal acetylenes undergo this process to produce excellent yields of 3-iodoindoles. The reactivity of the carbon-nitrogen bond cleavage during cyclization follows the following order: Me > n-Bu, Me > Ph, and cyclohexyl > Me. Subsequent palladium-catalyzed Sonogashira, Suzuki, and Heck reactions of the resulting 3-iodoindoles proceed smoothly in good yields.

Sudestada1, a Drosophila ribosomal prolyl-hydroxylase required for mRNA translation, cell homeostasis, and organ growth

PubMed Central

Katz, Maximiliano J.; Acevedo, Julieta M.; Loenarz, Christoph; Galagovsky, Diego; Liu-Yi, Phebee; Pérez-Pepe, Marcelo; Thalhammer, Armin; Sekirnik, Rok; Ge, Wei; Melani, Mariana; Thomas, María G.; Simonetta, Sergio; Boccaccio, Graciela L.; Schofield, Christopher J.; Cockman, Matthew E.; Ratcliffe, Peter J.; Wappner, Pablo

2014-01-01

Genome sequences predict the presence of many 2-oxoglutarate (2OG)-dependent oxygenases of unknown biochemical and biological functions in Drosophila. Ribosomal protein hydroxylation is emerging as an important 2OG oxygenase catalyzed pathway, but its biological functions are unclear. We report investigations on the function of Sudestada1 (Sud1), a Drosophila ribosomal oxygenase. As with its human and yeast homologs, OGFOD1 and Tpa1p, respectively, we identified Sud1 to catalyze prolyl-hydroxylation of the small ribosomal subunit protein RPS23. Like OGFOD1, Sud1 catalyzes a single prolyl-hydroxylation of RPS23 in contrast to yeast Tpa1p, where Pro-64 dihydroxylation is observed. RNAi-mediated Sud1 knockdown hinders normal growth in different Drosophila tissues. Growth impairment originates from both reduction of cell size and diminution of the number of cells and correlates with impaired translation efficiency and activation of the unfolded protein response in the endoplasmic reticulum. This is accompanied by phosphorylation of eIF2α and concomitant formation of stress granules, as well as promotion of autophagy and apoptosis. These observations, together with those on enzyme homologs described in the companion articles, reveal conserved biochemical and biological roles for a widely distributed ribosomal oxygenase. PMID:24550463

α-MnO2 nanorods supported on porous graphitic carbon nitride as efficient electrocatalysts for lithium-air batteries

NASA Astrophysics Data System (ADS)

Hang, Yang; Zhang, Chaofeng; Luo, Xiaoman; Xie, Yingshen; Xin, Sen; Li, Yutao; Zhang, Dawei; Goodenough, John B.

2018-07-01

Synthesis of α-MnO2 nanorods grown on porous graphitic carbon nitride (g-C3N4) sheets via a facile hydrothermal treatment gives a porous composite exhibiting higher activity for an air cathode than the individual component of α-MnO2 or porous g-C3N4 for both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The porous g-C3N4/α-MnO2 composite also exhibits better performance in a Li-air battery than pure α-MnO2 or XC-72 carbon catalysts, which includes superior discharge capacity, low voltage gap and high cycle stability. The α-MnO2 nanorods catalyze the OER and the porous g-C3N4 sheets catalyze the ORR.

Synthesis of a biofuel target through conventional organic chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Page, Jordan P.; Robinson, Joshua W.; Albrecht, Karl O.

In this work, the biofuel target compound 2-ethyl-5,5-dimethylcyclopenta-1,3-diene (1) and its exo isomers (9a and 9b), were successfully synthesized via two different pathways from the common intermediate 4,4-dimethylcyclopent-2-ene-1-one (2). The first pathway produced the endocyclic product as a pure isomer via a triflate intermediate obtained from the ketone 2 in 60% yield, followed by copper catalyzed coupling with ethyl magnesium bromide in 63% yield. The second pathway employed a Grignard reaction with ketone 2, which generated an alcohol that was immediately subjected to mild acid catalyzed elimination upon workup of the previous step to yield a primarily a mixture ofmore » exo diastereomers 9a and 9b in 77% yield. These targets had their fuel properties characterized in a separate study.« less

Macrocyclic bis-thioureas catalyze stereospecific glycosylation reactions.

PubMed

Park, Yongho; Harper, Kaid C; Kuhl, Nadine; Kwan, Eugene E; Liu, Richard Y; Jacobsen, Eric N

2017-01-13

Carbohydrates are involved in nearly all aspects of biochemistry, but their complex chemical structures present long-standing practical challenges to their synthesis. In particular, stereochemical outcomes in glycosylation reactions are highly dependent on the steric and electronic properties of coupling partners; thus, carbohydrate synthesis is not easily predictable. Here we report the discovery of a macrocyclic bis-thiourea derivative that catalyzes stereospecific invertive substitution pathways of glycosyl chlorides. The utility of the catalyst is demonstrated in the synthesis of trans-1,2-, cis-1,2-, and 2-deoxy-β-glycosides. Mechanistic studies are consistent with a cooperative mechanism in which an electrophile and a nucleophile are simultaneously activated to effect a stereospecific substitution reaction. Copyright © 2017, American Association for the Advancement of Science.

Enantioselective photochemistry via Lewis acid catalyzed triplet energy transfer

PubMed Central

Blum, Travis R.; Miller, Zachary D.; Bates, Desiree M.; Guzei, Ilia A.; Yoon, Tehshik P.

2017-01-01

Relatively few catalytic systems are able to control the stereochemistry of electronically excited organic intermediates. Here we report the discovery that a chiral Lewis acid complex can catalyze triplet energy transfer from an electronically excited photosensitizer. This strategy is applied to asymmetric [2+2] photocycloadditions of 2′-hydroxychalcones using tris(bipyridyl) ruthenium(II) as a sensitizer. A variety of electrochemical, computational, and spectroscopic data rule out substrate activation via photoinduced electron transfer and instead support a mechanism in which Lewis acid coordination dramatically lowers the triplet energy of the chalcone substrate. We expect that this approach will enable chemists to more broadly apply their detailed understanding of chiral Lewis acid catalysis to stereocontrol in reactions of electronically excited states. PMID:27980203