Sample records for catalyzed c-c bond

  1. Ag-catalyzed C-H/C-C bond functionalization.


    Zheng, Qing-Zhong; Jiao, Ning


    Silver, known and utilized since ancient times, is a coinage metal, which has been widely used for various organic transformations in the past few decades. Currently, the silver-catalyzed reaction is one of the frontier areas in organic chemistry, and the progress of research in this field is very rapid. Compared with other transition metals, silver has long been believed to have low catalytic efficiency, and most commonly, it is used as either a cocatalyst or a Lewis acid. Interestingly, the discovery of Ag-catalysis has been significantly improved in recent years. Especially, Ag(i) has been demonstrated as an important and versatile catalyst for a variety of organic transformations. However, so far, there has been no systematic review on Ag-catalyzed C-H/C-C bond functionalization. In this review, we will focus on the development of Ag-catalyzed C-H/C-C bond functionalization and the corresponding mechanism. PMID:27056573

  2. Manganese-catalyzed regiospecific sp(3) C-S bond formation through C-C bond cleavage of cyclobutanols.


    Ren, Rongguo; Wu, Zhen; Zhu, Chen


    A manganese-catalyzed regioselective sp(3) C-S bond formation through C-C bond cleavage of cyclobutanols is described. A variety of primary and secondary alkyl thioethers are efficiently prepared under mild reaction conditions. The mechanistic pathways involving radical-mediated tandem C-C bond cleavage and C-S bond formation are proposed. PMID:27279018

  3. Rh(I)-Catalyzed Insertion of Allenes into C-C Bonds of Benzocyclobutenols.


    Zhao, Chunliang; Liu, Li-Chuan; Wang, Jing; Jiang, Chenran; Zhang, Qing-Wei; He, Wei


    Herein we report a Rh(I)-catalyzed two carbon insertion into C-C bonds of benzocyclobutenols by employing symmetrical and unsymmetrical allenes. This reaction provides rapid access to alkylidene tetralins bearing two adjacent stereogenic centers in good yields and diasteroselectivities. PMID:26727276

  4. Formation of C-C bonds via ruthenium-catalyzed transfer hydrogenation().


    Moran, Joseph; Krische, Michael J


    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C-C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  5. Formation of C-C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation.


    Bower, John F; Krische, Michael J


    The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds. PMID:21822399

  6. Formation of C-C Bonds via Iridium-Catalyzed Hydrogenation and Transfer Hydrogenation

    NASA Astrophysics Data System (ADS)

    Bower, John F.; Krische, Michael J.

    The formation of C-C bonds via catalytic hydrogenation and transfer hydrogenation enables carbonyl and imine addition in the absence of stoichiometric organometallic reagents. In this review, iridium-catalyzed C-C bond-forming hydrogenations and transfer hydrogenations are surveyed. These processes encompass selective, atom-economic methods for the vinylation and allylation of carbonyl compounds and imines. Notably, under transfer hydrogenation conditions, alcohol dehydrogenation drives reductive generation of organoiridium nucleophiles, enabling carbonyl addition from the aldehyde or alcohol oxidation level. In the latter case, hydrogen exchange between alcohols and π-unsaturated reactants generates electrophile-nucleophile pairs en route to products of hydro-hydroxyalkylation, representing a direct method for the functionalization of carbinol C-H bonds.

  7. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    SciTech Connect

    Colby, Denise; Bergman, Robert; Ellman, Jonathan


    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach that has

  8. Enantioselective Rh-Catalyzed Carboacylation of C═N Bonds via C-C Activation of Benzocyclobutenones.


    Deng, Lin; Xu, Tao; Li, Hongbo; Dong, Guangbin


    Herein we describe the first enantioselective Rh-catalyzed carboacylation of oximes (imines) via C-C activation. In this transformation, the benzocyclobutenone C1-C2 bond is selectively activated by a low valent rhodium catalyst and subsequently the resulting two Rh-C bonds add across a C═N bond, which provides a unique approach to access chiral lactams. A range of polycyclic nitrogen-containing scaffolds were obtained in good yields with excellent enantioselectivity. Further derivatization of the lactam products led to a rapid entry to various novel fused heterocycles. PMID:26674855

  9. Gold-Catalyzed Oxidation of Propargylic Ethers with Internal C-C Triple Bonds: Impressive Regioselectivity Enabled by Inductive Effect

    PubMed Central

    Ji, Kegong; D’Souza, Brendan; Nelson, Jon; Zhang, Liming


    Inductive perturbations of C-C triple bonds are shown to dictate the regiochemistry of gold-catalyzed oxidation of internal C-C triple bonds in the cases of propargylic ethers, resulting in highly regioselective formation of β-alkoxy-α,β-unsaturated ketones (up to >50/1 selectivity) via α-oxo gold carbene intermediates. Ethers derived from primary propargylic alcohols can be reliably transformed in good yields, and various functional groups are tolerated. With substrates derived from secondary propargylic alcohols, the development of a new P,N-bidentate ligand enables the minimization of competing alkyl group migration to the gold carbene center over the desired hydride migration; the preferred migration of a phenyl group, however, results in efficient formation of a α-phenyl-β-alkoxy-α,β-unsaturated ketone. These results further advance the surrogacy of a propargyl moiety to synthetically versatile enone function with reliable and readily predictable regioselectivity. PMID:25284890

  10. A Homogeneous, Recyclable Polymer Support for Rh(I)-Catalyzed C-C Bond Formation

    PubMed Central

    Jana, Ranjan; Tunge, Jon A.


    A robust and practical polymer-supported, homogeneous, recyclable biphephos rhodium(I) catalyst has been developed for C-C bond formation reactions. Control of polymer molecular weight allowed tuning of the polymer solubility such that the polymer-supported catalyst is soluble in nonpolar solvents and insoluble in polar solvents. Using the supported rhodium catalysts, addition of aryl and vinylboronic acids to the electrophiles such as enones, aldehydes, N-sulfonyl aldimines, and alkynes occurs smoothly to provide products in high yields. Additions of terminal alkynes to enones and industrially relevant hydroformylation reactions have also been successfully carried out. Studies show that the leaching of Rh from the polymer support is low and catalyst recycle can be achieved by simple precipitation and filtration. PMID:21895010

  11. Ceric ammonium nitrate (CAN) catalyzed modification of ketones via two C-C bond cleavages with the retention of the oxo-group.


    Feng, Peng; Sun, Xiang; Su, Yijin; Li, Xinyao; Zhang, Li He; Shi, Xiaodong; Jiao, Ning


    A simple ceric ammonium nitrate (CAN) catalyzed functionalization of ketones through double C-C bond cleavage strategy has been disclosed. This reaction provides a mild, practical method toward carbamoyl azides, which are versatile intermediates and building blocks in organic synthesis. Based on relevant mechanistic studies, a unique and plausible C-C bond and N-O bond cleavage process is proposed, where the oxyamination intermediate plays an important role in this reaction. PMID:24906031

  12. Palladium(ii)-catalyzed C-C and C-O bond formation for the synthesis of C1-benzoyl isoquinolines from isoquinoline N-oxides and nitroalkenes.


    Li, Jiu-Ling; Li, Wei-Ze; Wang, Ying-Chun; Ren, Qiu; Wang, Heng-Shan; Pan, Ying-Ming


    C1-Benzoyl isoquinolines can be generated via a palladium(ii)-catalyzed C-C and C-O coupling of isoquinoline N-oxides with aromatic nitroalkenes. The reaction proceeds through remote C-H bond activation and subsequent intramolecular oxygen atom transfer (OAT). In this reaction, the N-O bond was designed as a directing group in the C-H bond activation as well as the source of an oxygen atom. PMID:27443150

  13. Rhodium-catalyzed oxidative coupling of triarylmethanols with internal alkynes via successive C-H and C-C bond cleavages.


    Uto, Toshihiko; Shimizu, Masaki; Ueura, Kenji; Tsurugi, Hayato; Satoh, Tetsuya; Miura, Masahiro


    The rhodium-catalyzed oxidative coupling of triarylmethanols with internal alkynes effectively proceeds in a 1:2 manner via cleavage of C-H and C-C bonds to produce the corresponding naphthalene derivatives. Addition of tri- or tetraphenylcyclopentadiene as a ligand is crucial for the reaction to occur efficiently. PMID:18052297

  14. A Selective Rh(I) -Catalyzed Substrate-Controlled C-C Bond Activation of Benzyl Sulfonamide/Alcohol-Tethered Alkylidenecyclopropanes.


    Chen, Kai; Liu, Jia-Xin; Tang, Xiang-Ying; Shi, Min


    Benzyl sulfonamide/alcohol-tethered alkylidenecyclopropanes undergo a rhodium-catalyzed and substrate-controlled selective C-C bond activation, producing three types of common organic structural units: benzo[c]azepine/oxepines, dihydronaphthalen-1-amines, and conjugated dienes. Epoxidation and aromatization of these products to construct two useful compounds have also been achieved. PMID:27305281

  15. Rh(III)-Catalyzed Synthesis of N-Unprotected Indoles from Imidamides and Diazo Ketoesters via C-H Activation and C-C/C-N Bond Cleavage.


    Qi, Zisong; Yu, Songjie; Li, Xingwei


    The synthesis of N-unprotected indoles has been realized via Rh(III)-catalyzed C-H activation/annulation of imidamides with α-diazo β-ketoesters. The reaction occurs with the release of an amide coproduct, which originates from both the imidamide and the diazo as a result of C═N cleavage of the imidamide and C-C(acyl) cleavage of the diazo. A rhodacyclic intermediate has been isolated and a plausible mechanism has been proposed. PMID:26824751

  16. Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines.


    Wang, Min; Lu, Jianmin; Ma, Jiping; Zhang, Zhe; Wang, Feng


    Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented. PMID:26494312

  17. Ruthenium-Catalyzed Transfer Hydrogenation for C-C Bond Formation: Hydrohydroxyalkylation and Hydroaminoalkylation via Reactant Redox Pairs.


    Perez, Felix; Oda, Susumu; Geary, Laina M; Krische, Michael J


    Merging the chemistry of transfer hydrogenation and carbonyl or imine addition, a broad new family of redox-neutral or reductive hydrohydroxyalkylations and hydroaminomethylations have been developed. In these processes, hydrogen redistribution between alcohols and π-unsaturated reactants is accompanied by C-C bond formation, enabling direct conversion of lower alcohols to higher alcohols. Similarly, hydrogen redistribution between amines to π-unsaturated reactants results in direct conversion of lower amines to higher amines. Alternatively, equivalent products of hydrohydroxyalkylation and hydroaminomethylation may be generated through the reaction of carbonyl compounds or imines with π-unsaturated reactants under the conditions of 2-propanol-mediated reductive coupling. Finally, using vicinally dioxygenated reactants, that is, diol, ketols, or diones, successive transfer hydrogenative coupling occurs to generate 2 C-C bonds, resulting in products of formal [4+2] cycloaddition. PMID:27573275

  18. Splitting a Substrate into Three Parts: Gold-Catalyzed Nitrogenation of Alkynes by C-C and C≡C Bond Cleavage.


    Qin, Chong; Su, Yijin; Shen, Tao; Shi, Xiaodong; Jiao, Ning


    A gold-catalyzed nitrogenation of alkynes for the synthesis of carbamides and amino tetrazoles through C-C and C≡C bond cleavages is described. A diverse set of functionalized carbamide and amino tetrazole derivatives were selectively constructed under mild conditions. The chemoselectivity can be easily switched by the selection of the acid additives. The reaction is characterized by its broad substrate scope, direct construction of high value products, easy operation under air, and mild conditions at room temperature. This chemistry provides a way to transform alkynes by splitting the substrate into three parts. PMID:26494539

  19. An Electron-Poor C64 Nanographene by Palladium-Catalyzed Cascade C-C Bond Formation: One-Pot Synthesis and Single-Crystal Structure Analysis.


    Seifert, Sabine; Shoyama, Kazutaka; Schmidt, David; Würthner, Frank


    Herein, we report the one-pot synthesis of an electron-poor nanographene containing dicarboximide groups at the corners. We efficiently combined palladium-catalyzed Suzuki-Miyaura cross-coupling and dehydrohalogenation to synthesize an extended two-dimensional π-scaffold of defined size in a single chemical operation starting from N-(2,6-diisopropylphenyl)-4,5-dibromo-1,8-naphthalimide and a tetrasubstituted pyrene boronic acid ester as readily accessible starting materials. The reaction of these precursors under the conditions commonly used for Suzuki-Miyaura cross-coupling afforded a C64 nanographene through the formation of ten C-C bonds in a one-pot process. Single-crystal X-ray analysis unequivocally confirmed the structure of this unique extended aromatic molecule with a planar geometry. The optical and electrochemical properties of this largest ever synthesized planar electron-poor nanographene skeleton were also analyzed. PMID:27058998

  20. Bronsted-Evans-Polany relationships for C-C bond forming and C-C bond breaking reactions in thiamine-catalyzed decarboxylation of 2-keto acids using density functional theory.

    SciTech Connect

    Assary, R. S.; Broadbelt, L. J.; Curtiss, L. A.


    The concept of generalized enzyme reactions suggests that a wide variety of substrates can undergo enzymatic transformations, including those whose biotransformation has not yet been realized. The use of quantum chemistry to evaluate kinetic feasibility is an attractive approach to identify enzymes for the proposed transformation. However, the sheer number of novel transformations that can be generated makes this impractical as a screening approach. Therefore, it is essential to develop structure/activity relationships based on quantities that are more efficient to calculate. In this work, we propose a structure/activity relationship based on the free energy of binding or reaction of non-native substrates to evaluate the catalysis relative to that of native substrates. While Broensted-Evans-Polanyi (BEP) relationships such as that proposed here have found broad application in heterogeneous catalysis, their extension to enzymatic catalysis is limited. We report here on density functional theory (DFT) studies for C-C bond formation and C-C bond cleavage associated with the decarboxylation of six 2-keto acids by a thiamine-containing enzyme (EC and demonstrate a linear relationship between the free energy of reaction and the activation barrier. We then applied this relationship to predict the activation barriers of 17 chemically similar novel reactions. These calculations reveal that there is a clear correlation between the free energy of formation of the transition state and the free energy of the reaction, suggesting that this method can be further extended to predict the kinetics of novel reactions through our computational framework for discovery of novel biochemical transformations.

  1. Rhodium(III)-Catalyzed Directed ortho-C-H Bond Functionalization of Aromatic Ketazines via C-S and C-C Coupling.


    Wen, Jing; Wu, An; Wang, Mingyang; Zhu, Jin


    Described herein is a convenient and efficient method for sulfuration and olefination of aromatic ketazines via rhodium-catalyzed oxidative C-H bond activation. A range of substituted substrates are supported, and a possible mechanism is proposed according to experimental results of kinetic isotopic effect, reversibility studies, and catalysis of rhodacycle intermediate c1. PMID:26417874

  2. Metal-catalyzed C-C bond cleavage in alkanes: effects of methyl substitution on transition-state structures and stability.


    Flaherty, David W; Hibbitts, David D; Iglesia, Enrique


    Methyl substituents at C-C bonds influence hydrogenolysis rates and selectivities of acyclic and cyclic C2-C8 alkanes on Ir, Rh, Ru, and Pt catalysts. C-C cleavage transition states form via equilibrated dehydrogenation steps that replace several C-H bonds with C-metal bonds, desorb H atoms (H*) from saturated surfaces, and form λ H2(g) molecules. Activation enthalpies (ΔH(‡)) and entropies (ΔS(‡)) and λ values for (3)C-(x)C cleavage are larger than for (2)C-(2)C or (2)C-(1)C bonds, irrespective of the composition of metal clusters or the cyclic/acyclic structure of the reactants. (3)C-(x)C bonds cleave through α,β,γ- or α,β,γ,δ-bound transition states, as indicated by the agreement between measured activation entropies and those estimated for such structures using statistical mechanics. In contrast, less substituted C-C bonds involve α,β-bound species with each C atom bound to several surface atoms. These α,β configurations weaken C-C bonds through back-donation to antibonding orbitals, but such configurations cannot form with (3)C atoms, which have one C-H bond and thus can form only one C-M bond. (3)C-(x)C cleavage involves attachment of other C atoms, which requires endothermic C-H activation and H* desorption steps that lead to larger ΔH(‡) values but also larger ΔS(‡) values (by forming more H2(g)) than for (2)C-(2)C and (2)C-(1)C bonds, irrespective of alkane size (C2-C8) or cyclic/acyclic structure. These data and their mechanistic interpretation indicate that low temperatures and high H2 pressures favor cleavage of less substituted C-C bonds and form more highly branched products from cyclic and acyclic alkanes. Such interpretations and catalytic consequences of substitution seem also relevant to C-X cleavage (X = S, N, O) in desulfurization, denitrogenation, and deoxygenation reactions. PMID:24961991

  3. Metal- and Oxidant-Free Synthesis of Quinazolinones from β-Ketoesters with o-Aminobenzamides via Phosphorous Acid-Catalyzed Cyclocondensation and Selective C-C Bond Cleavage.


    Li, Zhongwen; Dong, Jianyu; Chen, Xiuling; Li, Qiang; Zhou, Yongbo; Yin, Shuang-Feng


    A general and efficient phosphorous acid-catalyzed cyclocondensation of β-ketoesters with o-aminobenzamides via selective C-C bond cleavage leading to quinazolinones is developed. This reaction proceeds smoothly under metal- and oxidant-free conditions, giving both 2-alkyl- and 2-aryl-substituted quinazolinones in excellent yields. This strategy can also be applied to the synthesis of other N-heterocycles, such as benzimidazoles and benzothiazoles. PMID:26339716

  4. NAD(P)H-Independent Asymmetric C=C Bond Reduction Catalyzed by Ene Reductases by Using Artificial Co-substrates as the Hydrogen Donor

    PubMed Central

    Winkler, Christoph K; Clay, Dorina; Entner, Marcello; Plank, Markus; Faber, Kurt


    To develop a nicotinamide-independent single flavoenzyme system for the asymmetric bioreduction of C=C bonds, four types of hydrogen donor, encompassing more than 50 candidates, were investigated. Six highly potent, cheap, and commercially available co-substrates were identified that (under the optimized conditions) resulted in conversions and enantioselectivities comparable with, or even superior to, those obtained with traditional two-enzyme nicotinamide adenine dinucleotide phosphate (NAD(P)H)-recycling systems. PMID:24382795

  5. Metal-catalyzed alpha-arylation of carbonyl and related molecules: novel trends in C-C bond formation by C-H bond functionalization.


    Johansson, Carin C C; Colacot, Thomas J


    Alpha-arylated carbonyl compounds are commonly occurring motifs in biologically interesting molecules and are therefore of high interest to the pharmaceutical industry. Conventional procedures for their synthesis often result in complications in scale-up, such as the use of stoichiometric amounts of toxic reagents and harsh reaction conditions. Over the last decade, significant efforts have been directed towards the development of metal-catalyzed alpha-arylations of carbonyl compounds as an alternative synthetic approach that operates under milder conditions. This Review summarizes the developments in this area to date, with a focus on how the substrate scope has been expanded through selection of the most appropriate synthetic method, such as the careful choice of ligands, precatalysts, bases, and reaction conditions. PMID:20058282

  6. Alkali metal mediated C-C bond coupling reaction

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto


    Metal catalyzed carbon-carbon (C-C) bond formation is one of the important reactions in pharmacy and in organic chemistry. In the present study, the electron and hole capture dynamics of a lithium-benzene sandwich complex, expressed by Li(Bz)2, have been investigated by means of direct ab-initio molecular dynamics method. Following the electron capture of Li(Bz)2, the structure of [Li(Bz)2]- was drastically changed: Bz-Bz parallel form was rapidly fluctuated as a function of time, and a new C-C single bond was formed in the C1-C1' position of Bz-Bz interaction system. In the hole capture, the intermolecular vibration between Bz-Bz rings was only enhanced. The mechanism of C-C bond formation in the electron capture was discussed on the basis of theoretical results.

  7. Tailored synthesis of various nanomaterials by using a graphene-oxide-based gel as a nanoreactor and nanohybrid-catalyzed C-C bond formation.


    Biswas, Abhijit; Banerjee, Arindam


    New graphene oxide (GO)-based hydrogels that contain vitamin B2/B12 and vitamin C (ascorbic acid) have been synthesized in water (at neutral pH value). These gel-based soft materials have been used to synthesize various metal nanoparticles, including Au, Ag, and Pd nanoparticles, as well as nanoparticle-containing reduced graphene oxide (RGO)-based nanohybrid systems. This result indicates that GO-based gels can be used as versatile reactors for the synthesis of different nanomaterials and hybrid systems on the nanoscale. Moreover, the RGO-based nanohybrid hydrogel with Pd nanoparticles was used as an efficient catalyst for C-C bond-formation reactions with good yields and showed high recyclability in Suzuki-Miyaura coupling reactions. PMID:25224859

  8. Hydroxide-catalyzed bonding

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung (Inventor)


    A method of bonding substrates by hydroxide-catalyzed hydration/dehydration involves applying a bonding material to at least one surface to be bonded, and placing the at least one surface sufficiently close to another surface such that a bonding interface is formed between them. A bonding material of the invention comprises a source of hydroxide ions, and may optionally include a silicate component, a particulate filling material, and a property-modifying component. Bonding methods of the invention reliably and reproducibly provide bonds which are strong and precise, and which may be tailored according to a wide range of possible applications. Possible applications for bonding materials of the invention include: forming composite materials, coating substrates, forming laminate structures, assembly of precision optical components, and preparing objects of defined geometry and composition. Bonding materials and methods of preparing the same are also disclosed.

  9. Electronic Structure and Bonding in Iron(II) and Iron(I) Complexes Bearing Bisphosphine Ligands of Relevance to Iron-Catalyzed C-C Cross-Coupling.


    Kneebone, Jared L; Fleischauer, Valerie E; Daifuku, Stephanie L; Shaps, Ari A; Bailey, Joseph M; Iannuzzi, Theresa E; Neidig, Michael L


    Chelating phosphines are effective additives and supporting ligands for a wide array of iron-catalyzed cross-coupling reactions. While recent studies have begun to unravel the nature of the in situ-formed iron species in several of these reactions, including the identification of the active iron species, insight into the origin of the differential effectiveness of bisphosphine ligands in catalysis as a function of their backbone and peripheral steric structures remains elusive. Herein, we report a spectroscopic and computational investigation of well-defined FeCl2(bisphosphine) complexes (bisphosphine = SciOPP, dpbz, (tBu)dppe, or Xantphos) and known iron(I) variants to systematically discern the relative effects of bisphosphine backbone character and steric substitution on the overall electronic structure and bonding within their iron complexes across oxidation states implicated to be relevant in catalysis. Magnetic circular dichroism (MCD) and density functional theory (DFT) studies demonstrate that common o-phenylene and saturated ethyl backbone motifs result in small but non-negligible perturbations to 10Dq(Td) and iron-bisphosphine bonding character at the iron(II) level within isostructural tetrahedra as well as in five-coordinate iron(I) complexes FeCl(dpbz)2 and FeCl(dppe)2. Notably, coordination of Xantphos to FeCl2 results in a ligand field significantly reduced relative to those of its iron(II) partners, where a large bite angle and consequent reduced iron-phosphorus Mayer bond orders (MBOs) could play a role in fostering the unique ability of Xantphos to be an effective additive in Kumada and Suzuki-Miyaura alkyl-alkyl cross-couplings. Furthermore, it has been found that the peripheral steric bulk of the SciOPP ligand does little to perturb the electronic structure of FeCl2(SciOPP) relative to that of the analogous FeCl2(dpbz) complex, potentially suggesting that differences in the steric properties of these ligands might be more important in

  10. Enantioselective Ruthenium Catalyzed Carbonyl Allylation via Alkyne-Alcohol C-C Bond Forming Transfer Hydrogenation: Allene Hydrometallation vs. Oxidative Coupling

    PubMed Central

    Liang, Tao; Nguyen, Khoa D.; Zhang, Wandi; Krische, Michael J.


    Chiral ruthenium(II) complexes modified by Josiphos ligands catalyze the reaction of alkynes with primary alcohols to form homoallylic alcohols with excellent control of regio-, diastereo- and enantioselectivity. These processes represent the first examples of enantioselective carbonyl allylation using alkynes as allylmetal equivalents. PMID:25734220

  11. A one-pot copper catalyzed biomimetic route to N-heterocyclic amides from methyl ketones via oxidative C-C bond cleavage.


    Subramanian, Parthasarathi; Indu, Satrajit; Kaliappan, Krishna P


    A direct one-pot Cu-catalyzed biomimetic oxidation of methyl ketones to pharmaceutically important N-heterocyclic amides is reported. The scope of the method is broad, scalable, and mild, and the reaction is tolerant with various acid, base sensitive functionalities with multiple heteroatoms and aryl halides. The extensive mechanistic studies suggest that this reaction follows the Luciferin-Luciferase-like pathway. PMID:25409417

  12. Ruthenium catalyzed C-C bond formation via transfer hydrogenation: branch-selective reductive coupling of allenes to paraformaldehyde and higher aldehydes.


    Ngai, Ming-Yu; Skucas, Eduardas; Krische, Michael J


    Under the conditions of ruthenium-catalyzed transfer hydrogenation employing 2-propanol as the terminal reductant, 1,1-disubstituted allenes 1a- h engage in reductive coupling to paraformaldehyde to furnish homoallylic alcohols 2a- h. Under identical transfer hydrogenation conditions, 1,1-disubstituted allenes engage in reductive coupling to aldehydes 3a- f to furnish homoallylic alcohols 4a- n. In all cases, reductive coupling occurs with branched regioselectivity to deliver homoallylic alcohols bearing all-carbon quaternary centers. PMID:18533665

  13. Ruthenium(0) Catalyzed Endiyne-α-Ketol [4+2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures via C-C Bond Forming Transfer Hydrogenation

    PubMed Central

    Saxena, Aakarsh; Perez, Felix; Krische, Michael J.


    Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of ruthenium(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C-C coupling occurs to generate products of [4+2] cycloaddition. The proposed catalytic mechanism involves consecutive alkyne-carbonyl oxidative couplings to form transient oxaruthana-cycles that suffer α-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures. PMID:25938947

  14. Understanding Rotation about a C=C Double Bond

    ERIC Educational Resources Information Center

    Barrows, Susan E.; Eberlein, Thomas H.


    The study focuses on the process and energetic cost of twisting around a C=C double bond and provides instructors with a simple vehicle for rectifying the common misrepresentation of C=C double bonds as rigid and inflexible. Discussions of cis and trans isomers of cycloalkenes are a good entry point for introducing students to the idea of a…

  15. Rhodium-catalyzed C-C coupling reactions via double C-H activation.


    Li, Shuai-Shuai; Qin, Liu; Dong, Lin


    Various rhodium-catalyzed double C-H activations are reviewed. These powerful strategies have been developed to construct C-C bonds, which might be widely embedded in complex aza-fused heterocycles, polycyclic skeletons and heterocyclic scaffolds. In particular, rhodium(iii) catalysis shows good selectivity and reactivity to functionalize the C-H bond, generating reactive organometallic intermediates in most of the coupling reactions. Generally, intermolecular, intramolecular and multi-component coupling reactions via double C-H activations with or without heteroatom-assisted chelation are discussed in this review. PMID:27099126

  16. Iron-Catalyzed C-C Cross-Couplings Using Organometallics.


    Guérinot, Amandine; Cossy, Janine


    Over the last decades, iron-catalyzed cross-couplings have emerged as an important tool for the formation of C-C bonds. A wide variety of alkenyl, aryl, and alkyl (pseudo)halides have been coupled to organometallic reagents, the most currently used being Grignard reagents. Particular attention has been devoted to the development of iron catalysts for the functionalization of alkyl halides that are generally challenging substrates in classical cross-couplings. The high functional group tolerance of iron-catalyzed cross-couplings has encouraged organic chemists to use them in the synthesis of bioactive compounds. Even if some points remain obscure, numerous studies have been carried out to investigate the mechanism of iron-catalyzed cross-coupling and several hypotheses have been proposed. PMID:27573401

  17. Copper-catalyzed domino synthesis of 2-imino-1H-imidazol-5(2H)-ones and quinoxalines involving C-C bond cleavage with a 1,3-dicarbonyl unit as a leaving group.


    Yang, Yan; Ni, Fan; Shu, Wen-Ming; Wu, An-Xin


    Although 2-imino-1H-imidazol-5(2H)-ones have important biological activities in metabolism, their synthesis has rarely been investigated. Quinoxalines as "privileged scaffolds" in medicinal chemistry have been extensively investigated, but the development of novel and efficient synthetic methods remains very attractive. Herein, we have developed two copper-catalyzed domino reactions for the synthesis of 2-imino-1H-imidazol-5(2H)-ones and quinoxalines involving CC bond-cleavage with a 1,3-dicarbonyl unit as a leaving group. The domino sequence for the synthesis of 2-imino-1H-imidazol-5(2H)-ones includes aza-Michael addition, intramolecular cyclization, CC bond-cleavage, 1,2-rearrangement, and aerobic dehydrogenation reaction, whereas the domino sequence for the synthesis of quinoxalines includes aza-Michael addition, intramolecular cyclization, elimination reaction, and CC bond-cleavage reaction. The two domino reactions have significant advantages including high efficiency, mild reaction conditions, and high tolerance of various functional groups. PMID:25079446

  18. Ni-Catalyzed C-C Couplings Using Alkyl Electrophiles.


    Iwasaki, Takanori; Kambe, Nobuaki


    Much effort has been devoted to developing new methods using Ni catalysts for the cross-coupling reaction of alkyl electrophiles with organometallic reagents, and significant achievements in this area have emerged during the past two decades. Nickel catalysts have enabled the coupling reaction of not only primary alkyl electrophiles, but also sterically hindered secondary and tertiary alkyl electrophiles possessing β-hydrogens with various organometallic reagents to construct carbon skeletons. In addition, Ni catalysts opened a new era of asymmetric cross-coupling reaction using alkyl halides. Recent progress in nickel-catalyzed cross-coupling reaction of alkyl electrophiles with sp(3)-, sp(2)-, and sp-hybridized organometallic reagents including asymmetric variants as well as mechanistic insights of nickel catalysis are reviewed in this chapter. PMID:27580894

  19. Metalloenzyme-Like Zeolites as Lewis Acid Catalysts for C-C Bond Formation.


    Van de Vyver, Stijn; Román-Leshkov, Yuriy


    The use of metalloenzyme-like zeolites as Lewis acid catalysts for C-C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass-derived compounds. The discovery of new Diels-Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl-ene reactions have given a further boost to this rapidly evolving field. PMID:26465652

  20. Direct, redox-neutral prenylation and geranylation of secondary carbinol C-H bonds: C4-regioselectivity in ruthenium-catalyzed C-C couplings of dienes to α-hydroxy esters.


    Leung, Joyce C; Geary, Laina M; Chen, Te-Yu; Zbieg, Jason R; Krische, Michael J


    The ruthenium catalyst generated in situ from Ru(3)(CO)(12) and tricyclohexylphosphine, PCy(3), promotes the redox-neutral C-C coupling of aryl-substituted α-hydroxy esters to isoprene and myrcene at the diene C4-position, resulting in direct carbinol C-H prenylation and geranylation, respectively. This process enables direct conversion of secondary to tertiary alcohols in the absence of stoichiometric byproducts or premetalated reagents, and is the first example of C4-regioselectivity in catalytic C-C couplings of 2-substituted dienes to carbonyl partners. Mechanistic studies corroborate a catalytic cycle involving diene-carbonyl oxidative coupling. PMID:22985393

  1. Rh(III)-Catalyzed C-C/C-N Coupling of Imidates with α-Diazo Imidamide: Synthesis of Isoquinoline-Fused Indoles.


    Wang, He; Li, Lei; Yu, Songjie; Li, Yunyun; Li, Xingwei


    Imidate esters and diazo compounds have been established as bifunctional substrates for the construction of biologically active fused heterocycles via rhodium-catalyzed C-H activation and C-C/C-N coupling. This reaction occurs under mild conditions with high efficiency, step economy, and low catalyst loading. PMID:27280947

  2. Template Catalysis by Metal-Ligand Cooperation. C-C Bond Formation via Conjugate Addition of Non-activated Nitriles under Mild, Base-free Conditions Catalyzed by a Manganese Pincer Complex.


    Nerush, Alexander; Vogt, Matthias; Gellrich, Urs; Leitus, Gregory; Ben-David, Yehoshoa; Milstein, David


    The first example of a catalytic Michael addition reaction of non-activated aliphatic nitriles to α,β-unsaturated carbonyl compounds under mild, neutral conditions is reported. A new de-aromatized pyridine-based PNP pincer complex of the Earth-abundant, first-row transition metal manganese serves as the catalyst. The reaction tolerates a variety of nitriles and Michael acceptors with different steric features and acceptor strengths. Mechanistic investigations including temperature-dependent NMR spectroscopy and DFT calculations reveal that the cooperative activation of alkyl nitriles, which leads to the generation of metalated nitrile nucleophile species (α-cyano carbanion analogues), is a key step of the mechanism. The metal center is not directly involved in the catalytic bond formation but rather serves, cooperatively with the ligand, as a template for the substrate activation. This approach of "template catalysis" expands the scope of potential donors for conjugate addition reactions. PMID:27164437

  3. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.


    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  4. Hydrogen induced C-C, C-N, and C-S bond activation on Pt and Ni surfaces

    SciTech Connect

    Gland, J.L.


    The work has focussed on hydrogen induced bond activation in adsorbed organic molecules and intermediates containin C-S and C-N and C-C bonds on Ni(100), Ni(111), and Pt(111) surfaces. Fluorescence Yield Near Edge Spectroscopy (FYNES) above the carbon K edge was used for adsorbed organic reactants and in-situ kinetic studies of bond activation. Results indicate that the activation is enhanced on Ni relative to Pt. Methylthiolate and methylamine adsorbed on Pt(111) were studied.

  5. Stereochemistry of enzymatic water addition to C=C bonds.


    Chen, Bi-Shuang; Otten, Linda G; Hanefeld, Ulf


    Water addition to carbon-carbon double bonds using hydratases is attracting great interest in biochemistry. Most of the known hydratases are involved in primary metabolism and to a lesser extent in secondary metabolism. New hydratases have recently been added to the toolbox, both from natural sources or artificial metalloenzymes. In order to comprehensively understand how the hydratases are able to catalyse the water addition to carbon-carbon double bonds, this review will highlight the mechanistic and stereochemical studies of the enzymatic water addition to carbon-carbon double bonds, focusing on the syn/anti-addition and stereochemistry of the reaction. PMID:25640045

  6. Iterative reactions of transient boronic acids enable sequential C-C bond formation

    NASA Astrophysics Data System (ADS)

    Battilocchio, Claudio; Feist, Florian; Hafner, Andreas; Simon, Meike; Tran, Duc N.; Allwood, Daniel M.; Blakemore, David C.; Ley, Steven V.


    The ability to form multiple carbon-carbon bonds in a controlled sequence and thus rapidly build molecular complexity in an iterative fashion is an important goal in modern chemical synthesis. In recent times, transition-metal-catalysed coupling reactions have dominated in the development of C-C bond forming processes. A desire to reduce the reliance on precious metals and a need to obtain products with very low levels of metal impurities has brought a renewed focus on metal-free coupling processes. Here, we report the in situ preparation of reactive allylic and benzylic boronic acids, obtained by reacting flow-generated diazo compounds with boronic acids, and their application in controlled iterative C-C bond forming reactions is described. Thus far we have shown the formation of up to three C-C bonds in a sequence including the final trapping of a reactive boronic acid species with an aldehyde to generate a range of new chemical structures.

  7. Palladium-catalyzed cross-dehydrogenative functionalization of C(sp(2))-H Bonds.


    Wu, Yinuo; Wang, Jun; Mao, Fei; Kwong, Fuk Yee


    The catalytic cross-dehydrogenative coupling (CDC) reaction has received intense attention in recent years. The attractive feature of this coupling process is the formation of a C-C bond from two C-H moieties under oxidative conditions. In this Focus Review, recent advances in the palladium-catalyzed CDC reactions of C(sp(2) )-H bond are summarized, with a focus on the period from 2011 to early 2013. PMID:24123795

  8. Palladium-Catalyzed Deaminative Phenanthridinone Synthesis from Aniline via C-H Bond Activation.


    Yedage, Subhash L; Bhanage, Bhalchandra M


    This work reports palladium-catalyzed phenanthridinone synthesis using the coupling of aniline and amide by formation of C-C and C-N bonds in a one-pot fashion via dual C-H bond activation. It involves simultaneous cleavage of four bonds and the formation of two new bonds. The present protocol is ligand-free, takes place under mild reaction conditions, and is environmentally benign as nitrogen gas and water are the only side products. This transformation demonstrates a broad range of aniline and amide substrates with different functional groups and has been scaled up to gram level. PMID:27088815

  9. Synthesis of 2-Benzylphenyl Ketones by Aryne Insertion into Unactivated C-C Bonds.


    Rao, Bin; Tang, Jinghua; Zeng, Xiaoming


    A transition-metal-free procedure to access to functionalized 2-benzylphenyl ketones is described by direct insertion of arynes into benzylic C-C bonds. This reaction was promoted by cesium fluoride at room temperature, allowing the products to form in high selectivity and achieve good functional group tolerance. PMID:27004731

  10. Facile P-C/C-H Bond-Cleavage Reactivity of Nickel Bis(diphosphine) Complexes.


    Zhang, Shaoguang; Li, Haixia; Appel, Aaron M; Hall, Michael B; Bullock, R Morris


    Unusual cleavage of P-C and C-H bonds of the P2 N2 ligand, in heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes under mild conditions, results in the formation of an iminium formyl nickelate featuring a C,P,P-tridentate coordination mode. The structures of both the heteroleptic [Ni(P2 N2 )(diphosphine)](2+) complexes and the resulting iminium formyl nickelate have been characterized by NMR spectroscopy and single-crystal X-ray diffraction analysis. Density functional theory (DFT) calculations were employed to investigate the mechanism of the P-C/C-H bond cleavage, which involves C-H bond cleavage, hydride rotation, Ni-C/P-H bond formation, and P-C bond cleavage. PMID:27189413

  11. [Hydrogen induced C-C, C-N, and C-S bond activities on Pi and Ni surfaces]: Summary

    SciTech Connect

    Gland, J.L.


    This document summarizes research applied to chemical bond activation studies. Topics summarized include: Carbon nitrogen bonds experimentation with aniline on Ni(111), Mi(100), and Pt(111) surfaces; carbon sulfur bonds experimentation with methanethiol, phenylthiol, and dimethyl disulfide on Pt(111) and Ni(111) surfaces; carbon-carbon bonds experimentation on Ni(100), Ni(111) and Pt(111) surfaces; and in-situ fluorescence yield near edge spectroscopy.

  12. Baeyer-Villiger C-C bond cleavage reaction in gilvocarcin and jadomycin biosynthesis

    PubMed Central

    Tibrewal, Nidhi; Pahari, Pallab; Wang, Guojun; Kharel, Madan K.; Morris, Caleb; Downey, Theresa; Hou, Yanpeng; Bugni, Tim S.; Rohr, Jürgen


    GilOII has been unambiguously identified as the key enzyme performing the crucial C-C bond cleavage reaction responsible for the unique rearrangement of a benz[a]anthracene skeleton to the benzo[d]naphthopyranone backbone typical for the gilvocarcin type natural anticancer antibiotics. Further investigations of this enzyme led to the isolation of a hydroxy-oxepinone intermediate which allowed important conclusions regarding the cleavage mechanism. PMID:23102024

  13. Aerobic synthesis of substituted quinoline from aldehyde and aniline: copper-catalyzed intermolecular C-H active and C-C formative cyclization.


    Yan, Rulong; Liu, Xingxing; Pan, Congming; Zhou, Xiaoqiang; Li, Xiaoni; Kang, Xing; Huang, Guosheng


    An efficient method for the direct synthesis of substituted quinolines from anilines and aldehydes through C-H functionalization, C-C/C-N bond formation, and C-C bond cleavage has been developed. The method is simple and practical and employs air as an oxidant. PMID:24024912

  14. Palladium-Catalyzed Synthesis of Phenanthridine/Benzoxazine-Fused Quinazolinones by Intramolecular C-H Bond Activation.


    Gupta, Puneet K; Yadav, Nisha; Jaiswal, Subodh; Asad, Mohd; Kant, Ruchir; Hajela, Kanchan


    A highly efficient synthesis of phenanthridine/benzoxazine-fused quinazolinones by ligand-free palladium-catalyzed intramolecular C-H bond activation under mild conditions has been developed. The C-C coupling provides the corresponding N-fused polycyclic heterocycles in good to excellent yields and with wide functional group tolerance. PMID:26230355

  15. Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.


    Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen


    A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct. PMID:26698150

  16. The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.


    The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2.

  17. Direct construction of 2-alkylbenzo-1,3-azoles via C-H activation of alkanes for C-C and C-X (X = O, S) bond formation.


    Yadav, Arvind K; Yadav, Lal Dhar S


    Copper catalyzed straightforward synthesis of 2-alkylbenzoxa(thia)azoles from aryl isocyanates/isothiocyanates and simple alkanes is reported. The protocol utilizes ditertiary butyl peroxide (DTBP) as a radical initiator and involves sequential formation of C-C and C-X (X = O, S) bonds followed by aromatization in a one-pot procedure. PMID:25578954

  18. Comparison of the kinetics and thermodynamics for methyl radical addition to C=C, C=O, and C=S double bonds.


    Henry, David J; Coote, Michelle L; Gómez-Balderas, Rodolfo; Radom, Leo


    The barriers, enthalpies, and rate constants for the addition of methyl radical to the double bonds of a selection of alkene, carbonyl, and thiocarbonyl species (CH(2)=Z, CH(3)CH=Z, and (CH(3))(2)C=Z, where Z = CH(2), O, or S) and for the reverse beta-scission reactions have been investigated using high-level ab inito calculations. The results are rationalized with the aid of the curve-crossing model. The addition reactions proceed via early transition structures in all cases. The barriers for addition of methyl radical to C=C bonds are largely determined by the reaction exothermicities. Addition to the unsubstituted carbon center of C=C double bonds is favored over addition to the substituted carbon center, both kinetically (lower barriers) and thermodynamically (greater exothermicities). The barriers for addition to C=O bonds are influenced by both the reaction exothermicity and the singlet-triplet gap of the substrate. Addition to the carbon center is favored over addition to the oxygen, also both thermodynamically and kinetically. For the thiocarbonyl systems, addition to the carbon center is thermodynamically favored over addition to sulfur. However, in this case, the reaction is contrathermodynamic, addition to the sulfur center having a lower barrier due to spin density considerations. Entropic differences among corresponding addition and beta-scission reactions are relatively minor, and the differences in reaction rates are thus dominated by differences in the respective reaction barriers. PMID:14871104

  19. Unexpected copper-catalyzed aerobic oxidative cleavage of C(sp3)-C(sp3) bond of glycol ethers.


    Liu, Zhong-Quan; Zhao, Lixing; Shang, Xiaojie; Cui, Zili


    An unexpected Cu-catalyzed oxidative cleavage of the C(sp(3))-C(sp(3)) bond in glycol ethers by using air or molecular oxygen as the terminal stoichiometric oxidant is demonstrated. As a result, the corresponding α-acyloxy ethers and formates of 1,2-ethanediol are formed by direct coupling of carboxylic acids and aldehydes with glycol ethers under the reaction conditions. This method represents the first example of Cu-catalyzed aerobic cleavage of saturated C-C bond in ethers. PMID:22668348

  20. The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.


    The bond dissociation energies (De) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of De with respect to the one-particle basis is studied at the single-reference modified coupled-pair-functional (MCPF)level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration-interaction (MRCI) De values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size-extensive averaged-coupled-pair-functional (ACPF) method. The full-valence complete-active-space self-consistent-field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds.

  1. Recent Advances in Transition-Metal-Free Oxygenation of Alkene C=C Double Bonds for Carbonyl Generation.


    Wan, Jie-Ping; Gao, Yong; Wei, Li


    Carbonyl-forming reactions are a class of fundamental transformations in organic chemistry. Guided by the current importance of environmentally benign metal-free catalysis and synthesis, herein we review recent advances in carbonyl-generation reactions based on alkene C=C double oxygenation as well as related cascade reactions in the synthesis of diverse organic products. The content of this focus review consists of two important but different reaction models: oxygenation based on full C=C double-bond cleavage and oxygenation based on partial C=C double-bond cleavage. PMID:27237866

  2. Silver(I) NHC mediated C-C bond activation of alkyl nitriles and catalytic efficiency in oxazoline synthesis.


    Heath, Rachael; Müller-Bunz, Helge; Albrecht, Martin


    Preparation of silver triazolylidene (trz) species from triazolium salts and Ag2O in refluxing MeCN leads to a selective C-C bond cleavage and the formation of complexes of general formula [(trz)Ag(CN)] from Calkyl-CN bond activation. Moreover, these silver carbene complexes are precursors of highly active catalysts for oxazoline formation via aldol condensation. PMID:25913007

  3. Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.


    Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei


    A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures. PMID:27240114

  4. Surface-catalyzed C-C covalent coupling strategies toward the synthesis of low-dimensional carbon-based nanostructures.


    Fan, Qitang; Gottfried, J Michael; Zhu, Junfa


    Carbon-based nanostructures have attracted tremendous interest because of their versatile and tunable properties, which depend on the bonding type of the constituting carbon atoms. Graphene, as the most prominent representative of the π-conjugated carbon-based materials, consists entirely of sp(2)-hybridized carbon atoms and exhibits a zero band gap. Recently, countless efforts were made to open and tune the band gap of graphene for its applications in semiconductor devices. One promising method is periodic perforation, resulting in a graphene nanomesh (GNM), which opens the band gap while maintaining the exceptional transport properties. However, the typically employed lithographic approach for graphene perforation is difficult to control at the atomic level. The complementary bottom-up method using surface-assisted carbon-carbon (C-C) covalent coupling between organic molecules has opened up new possibilities for atomically precise fabrication of conjugated nanostructures like GNM and graphene nanoribbons (GNR), although with limited maturity. A general drawback of the bottom-up approach is that the desired structure usually does not represent the global thermodynamic minimum. It is therefore impossible to improve the long-range order by postannealing, because once the C-C bond formation becomes reversible, graphene as the thermodynamically most stable structure will be formed. This means that only carefully chosen precursors and reaction conditions can lead to the desired (non-graphene) material. One of the most popular and frequently used organic reactions for on-surface C-C coupling is the Ullmann reaction of aromatic halides. While experimentally simple to perform, the irreversibility of the C-C bond formation makes it a challenge to obtain long-range ordered nanostructures. With no postreaction structural improvement possible, the assembly process must be optimized to result in defect-free nanostructures during the initial reaction, requiring complete

  5. Alkyne-aldehyde reductive C-C coupling through ruthenium-catalyzed transfer hydrogenation: direct regio- and stereoselective carbonyl vinylation to form trisubstituted allylic alcohols in the absence of premetallated reagents.


    Leung, Joyce C; Patman, Ryan L; Sam, Brannon; Krische, Michael J


    Nonsymmetric 1,2-disubstituted alkynes engage in reductive coupling to a variety of aldehydes under the conditions of ruthenium-catalyzed transfer hydrogenation by employing formic acid as the terminal reductant and delivering the products of carbonyl vinylation with good to excellent levels of regioselectivity and with complete control of olefin stereochemistry. As revealed in an assessment of the ruthenium counterion, iodide plays an essential role in directing the regioselectivity of C-C bond formation. Isotopic labeling studies corroborate reversible catalytic propargyl C-H oxidative addition in advance of the C-C coupling, and demonstrate that the C-C coupling products do not experience reversible dehydrogenation by way of enone intermediates. This transfer hydrogenation protocol enables carbonyl vinylation in the absence of stoichiometric metallic reagents. PMID:21953608

  6. Central C-C Bonding Increases Optical and Chemical Stability of NIR Fluorophores

    PubMed Central

    Hyun, Hoon; Owens, Eric A.; Narayana, Lakshminarayana; Wada, Hideyuki; Gravier, Julien; Bao, Kai; Frangioni, John V.; Choi, Hak Soo; Henary, Maged


    Functional near-infrared (NIR) fluorophores have played a major role in the recent advances in bioimaging. However, the optical and physicochemical stabilities of NIR fluorophores in the biological and physiological environment are still a challenge. Especially, the ether linkage on the meso carbon of heptamethine core is fragile when exposed to serum proteins or other amine-rich biomolecules. To solve such a structural limitation, a rigid carbon-carbon bond was installed onto the framework of ether-linked NIR fluorophores through the Suzuki coupling. The robust fluorophores replaced as ZW800-1C and ZW800-3C displayed enhanced optical and chemical stability in various solvents and a 100% warm serum environment (> 99%, 24 h). The biodistribution and clearance of C-C coupled ZW800 compounds were almost identical to the previously developed oxygen-substituted ZW800 compounds. When conjugated with a small molecule ligand, ZW800-1C maintained the identical stable form in warm serum (>98%, 24 h), while ZW800-1A hydrolyzed quickly after 4 h incubation (34%, 24 h). PMID:25530846

  7. Spectroscopic Characterization of Lanthanum-Mediated Dehydrogenation and C-C Bond Coupling of Ethylene.


    Kumari, Sudesh; Cao, Wenjin; Zhang, Yuchen; Roudjane, Mourad; Yang, Dong-Sheng


    La(C2H2) and La(C4H6) are observed from the reaction of laser-vaporized La atoms with ethylene molecules by photoionization time-of-flight mass spectrometry and characterized by mass-analyzed threshold ionization spectroscopy. La(C2H2) is identified as a metallacyclopropene and La(C4H6) as a metallacyclopentene. The three-membered ring is formed by concerted H2 elimination and the five-membered cycle by dehydrogenation and C-C bond coupling. Both metallacycles prefer a doublet ground state with a La 6s-based unpaired electron. Ionization of the neutral doublet state of either complex produces a singlet ion state by removing the La-based electron. The ionization allows accurate measurements of the adiabatic ionization energy of the neutral doublet state and metal-ligand and ligand-based vibrational frequencies of the neutral and ionic states. Although the La atom is in a formal oxidation state of +2, the ionization energies of these metal-hydrocarbon cycles are lower than that of the neutral La atom. Deuteration has a small effect on the ionization energies of the two cyclic radicals but distinctive effects on their vibrational frequencies. PMID:27322131

  8. Bonding by Hydroxide-Catalyzed Hydration and Dehydration

    NASA Technical Reports Server (NTRS)

    Gwo, Dz-Hung


    A simple, inexpensive method for bonding solid objects exploits hydroxide-catalyzed hydration and dehydration to form silicate-like networks in thin surface and interfacial layers between the objects. The method can be practiced at room temperature or over a wide range of temperatures. The method was developed especially to enable the formation of precise, reliable bonds between precise optical components. The bonds thus formed exhibit the precision and transparency of bonds formed by the conventional optical-contact method and the strength and reliability of high-temperature frit bonds. The method also lends itself to numerous non-optical applications in which there are requirements for precise bonds and/or requirements for bonds, whether precise or imprecise, that can reliably withstand severe environmental conditions. Categories of such non-optical applications include forming composite materials, coating substrates, forming laminate structures, and preparing objects of defined geometry and composition. The method is applicable to materials that either (1) can form silicate-like networks in the sense that they have silicate-like molecular structures that are extensible into silicate-like networks or (2) can be chemically linked to silicate-like networks by means of hydroxide-catalyzed hydration and dehydration. When hydrated, a material of either type features surface hydroxyl (-OH) groups. In this method, a silicate-like network that bonds two substrates can be formed either by a bonding material alone or by the bonding material together with material from either or both of the substrates. Typically, an aqueous hydroxide bonding solution is dispensed and allowed to flow between the mating surfaces by capillary action. If the surface figures of the substrates do not match precisely, bonding could be improved by including a filling material in the bonding solution. Preferably, the filling material should include at least one ingredient that can be hydrated to

  9. Access to Structurally Diverse Quinoline-Fused Heterocycles via Rhodium(III)-Catalyzed C-C/C-N Coupling of Bifunctional Substrates.


    Yu, Songjie; Li, Yunyun; Zhou, Xukai; Wang, He; Kong, Lingheng; Li, Xingwei


    Rhodium(III)-catalyzed C-H activation of heteroarenes and functionalization with bifunctional substrates such as anthranils allows facile construction of quinoline-fused heterocycles under redox-neutral conditions. The couplings feature broad substrate scope and provide step-economical access to two classes of quinoline-fused condensed heterocycles. PMID:27267178

  10. Acceptorless dehydrogenation of C-C single bonds adjacent to functional groups by metal-ligand cooperation.


    Kusumoto, Shuhei; Akiyama, Midori; Nozaki, Kyoko


    Unprecedented direct acceptorless dehydrogenation of C-C single bonds adjacent to functional groups to form α,β-unsaturated compounds has been accomplished by using a new class of group 9 metal complexes. Metal-ligand cooperation operated by the hydroxycyclopentadienyl ligand was proposed to play a major role in the catalytic transformation. PMID:24299029

  11. Transition Metals Catalyzed Element-Cyano Bonds Activations

    PubMed Central

    Wang, Rui; Falck, John R.


    Cyano group as a versatile functionalized intermediate has been explored for several decades, as it readily transfers to many useful functionalization groups such as amine, amide, acid, etc., which make it possess high popularization and use value in organic synthesis. Reactions involved with element-cyano bond cleavage can provide not only a new cyano group but also a freshly functionalized skeleton in one-pot, consequently making it of high importance. The highlights reviewed herein include H-CN, Si-CN, C-CN, B-CN, Sn-CN, Ge-CN, S-CN, Halo-CN, N-CN, and O-CN bonds cleavages and will summarize progress in such an important research area. This review article will focus on transition metal catalyzed reactions involving element-cyano bond activation. PMID:25558119

  12. Total synthesis of protosappanin A and its derivatives via palladium catalyzed ortho C-H activation/C-C cyclization under microwave irradiation.


    Liu, Jiaqi; Zhou, Xuan; Wang, Chenglong; Fu, Wanyong; Chu, Wenyi; Sun, Zhizhong


    A total synthesis method for protosappanin A, which is a complex natural product with many biological activities, was developed with 6 linear steps. Dibenzo[b,d]oxepinones as the key intermediates of the synthetic route were prepared by a palladium-catalyzed ortho C-H activation/C-C cyclization under microwave irradiation. 25 derivatives of protosappanin A were obtained. PMID:26997503

  13. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.


    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A


    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  14. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.


    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno


    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation. PMID:23505625

  15. A quantum chemical topological analysis of the C-C bond formation in organic reactions involving cationic species.


    Domingo, Luis R; Pérez, Patricia


    ELF topological analysis of the ionic Diels-Alder (I-DA) reaction between the N,N-dimethyliminium cation and cyclopentadiene (Cp) has been performed in order to characterise the C-C single bond formation. The C-C bond formation begins in the short range of 2.00-1.96 Åvia a C-to-C pseudoradical coupling between the most electrophilic center of the iminium cation and one of the two most nucleophilic centers of Cp. The electron density of the pseudoradical center generated at the most electrophilic carbon of the iminium cation comes mainly from the global charge transfer which takes place along the reaction. Analysis of the global reactivity indices indicates that the very high electrophilic character of the iminium cation is responsible for the negative activation energy found in the gas phase. On the other hand, the analysis of the radical P(k)(o) Parr functions of the iminium cation, and the nucleophilic P(k)(-) Parr functions of Cp makes the characterisation of the most favourable two-center interaction along the formation of the C-C single bond possible. PMID:24901220

  16. Formation of C-C and C-O bonds and oxygen removal in reactions of alkanediols, alkanols, and alkanals on copper catalysts.


    Sad, María E; Neurock, Matthew; Iglesia, Enrique


    This study reports evidence for catalytic deoxygenation of alkanols, alkanals, and alkanediols on dispersed Cu clusters with minimal use of external H(2) and with the concurrent formation of new C-C and C-O bonds. These catalysts selectively remove O-atoms from these oxygenates as CO or CO(2) through decarbonylation or decarboxylation routes, respectively, that use C-atoms present within reactants or as H(2)O using H(2) added or formed in situ from CO/H(2)O mixtures via water-gas shift. Cu catalysts fully convert 1,3-propanediol to equilibrated propanol-propanal intermediates that subsequently form larger oxygenates via aldol-type condensation and esterification routes without detectable involvement of the oxide supports. Propanal-propanol-H(2) equilibration is mediated by their chemisorption and interconversion at surfaces via C-H and O-H activation and propoxide intermediates. The kinetic effects of H(2), propanal, and propanol pressures on turnover rates, taken together with measured selectivities and the established chemical events for base-catalyzed condensation and esterification reactions, indicate that both reactions involve kinetically relevant bimolecular steps in which propoxide species, acting as the base, abstract the α-hydrogen in adsorbed propanal (condensation) or attack the electrophilic C-atom at its carbonyl group (esterification). These weakly held basic alkoxides render Cu surfaces able to mediate C-C and C-O formation reactions typically catalyzed by basic sites inherent in the catalyst, instead of provided by coadsorbed organic moieties. Turnover rates for condensation and esterification reactions decrease with increasing Cu dispersion, because low-coordination corner and edge atoms prevalent on small clusters stabilize adsorbed intermediates and increase the activation barriers for the bimolecular kinetically relevant steps required for both reactions. PMID:22023723

  17. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.


    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier


    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity. PMID:27276418

  18. Unlocking Hydrogenation for C-C Bond Formation: A Brief Overview of Enantioselective Methods

    PubMed Central

    Hassan, Abbas; Krische, Michael J.


    Hydrogenation of π-unsaturated reactants in the presence of carbonyl compounds or imines promotes reductive C-C coupling, providing a byproduct-free alternative to stoichiometric organometallic reagents in an ever-increasing range of C=X (X = O, NR) additions. Under transfer hydrogenation conditions, hydrogen exchange between alcohols and π-unsaturated reactants triggers generation of electrophile-nucleophile pairs, enabling carbonyl addition directly from the alcohol oxidation level, bypassing discrete alcohol oxidation and generation of stoichiometric byproducts. PMID:22125398

  19. Molecular dynamics simulation of C-C bond scission in polyethylene and linear alkanes: effects of the condensed phase.


    Popov, Konstantin V; Knyazev, Vadim D


    The reaction of C-C bond scission in polyethylene chains of various lengths was studied using molecular dynamics under the conditions of vacuum and condensed phase (polymer melt). A method of assigning meaningful rate constant values to condensed-phase bond scission reactions based on a kinetic mechanism accounting for dissociation, reverse recombination, and diffusional separation of fragments was developed. The developed method accounts for such condensed-phase phenomena as cage effects and diffusion of the decay products away from the reaction site. The results of C-C scission simulations indicate that per-bond rate constants decrease by an order of magnitude as the density of the system increases from vacuum to the normal density of a polyethylene melt. Additional calculations were performed to study the dependence of the rate constant on the length of the polymer chain under the conditions of the condensed phase. The calculations demonstrate that the rate constant is independent of the degree of polymerization if polyethylene samples of different lengths are kept at the same pressure. However, if instead molecular systems of different polyethylene chain lengths decompose under the conditions of the same density, shorter chains result in higher pressures and lower rate constants. The observed effect is attributed to a higher degree of molecular crowding (lower fraction of free intermolecular space available for molecular motion) in the case of shorter molecules. PMID:24571517

  20. Rhodium(III)-catalyzed C-C coupling of 7-azaindoles with vinyl acetates and allyl acetates.


    Li, Shuai-Shuai; Wang, Cheng-Qi; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin


    The behaviour of electron-rich alkenes with 7-azaindoles in rhodium(III)-catalyzed C-H activation is investigated. Various substituted vinyl acetates and allyl acetates as coupling partners reacted smoothly providing a wide variety of 7-azaindole derivatives, and the selectivity of the coupling reaction is alkene-dependent. In addition, the approaches of rhodium(III)-catalyzed dehydrogenative Heck-type reaction (DHR) and carbonylation reaction were quite novel and simple. PMID:26553424

  1. Ternary Electrocatalysts for Oxidizing Ethanol to Carbon Dioxide: Making Ir Capable of Splitting C-C bond

    SciTech Connect

    Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, N.; More, Karren Leslie; Adzic, Radoslav R.


    Splitting the C-C bond is the main obstacle to electroxidation of ethanol (EOR) to CO2. We recently demonstrated that the ternary PtRhSnO2 electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We synthesized, characterized and compared the properties of several ternary electrocatalysts. Carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO2 NP core decorated with multi-metallic nanoislands (MM = PtIr, PtRh, IrRh, PtIrRh) were prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM /SnO2 NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity towards CO2 formation of several of these MM /SnO2/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO2/C catalysts. We demonstrate that the PtIr/SnO2/C catalyst with high Ir content shows outstanding catalytic property with the most negative EOR onset potential and reasonably good selectivity towards ethanol complete oxidation to CO2. PtRh/SnO2/C catalysts with a moderate Rh content exhibit the highest EOR selectivity, as deduced from infrared studies.

  2. Matching plasmon resonances to the C=C and C-H bonds in estradiol

    NASA Astrophysics Data System (ADS)

    Mbomson, Ifeoma G.; McMeekin, Scott; De La Rue, Richard; Johnson, Nigel P.


    We tune nanoantennas to resonate within mid-infrared wavelengths to match the vibrational resonances of C=C and C-H of the hormone estradiol. Modelling and fabrication of the nanoantennas produce plasmon resonances between 2 μm to 7 μm. The hormone estradiol was dissolved in ethanol and evaporated, leaving thickness of a few hundreds of nanometres on top of gold asymmetric split H-like shaped on a fused silica substrate. The reflectance was measured and a red-shift is recorded from the resonators plasmonic peaks. Fourier transform infrared spectroscopy is use to observe enhanced spectra of the stretching modes for the analyte which belongs to alkenyl biochemical group.

  3. Direct Construction of 4-Hydroxybenzils via Para-Selective C-C Bond Coupling of Phenols and Aryl Methyl Ketones.


    Xiang, Jia-Chen; Cheng, Yan; Wang, Miao; Wu, Yan-Dong; Wu, An-Xin


    A highly para-selective C-C bond coupling is presented between phenols C(sp(2)) and aryl methyl ketones C(sp(3)), which enables the direct construction of 4-hydroxybenzil derivatives. This practical method exhibits a broad substrate scope and large-scale applicability and represents a general gateway to the hydroxybenzil natural product family. Mechanistic investigations indicated that the combination of HI with DMSO realized the oxidative carbonylation of aryl methyl ketones, while boric acid acted as a dual-functional relay reagent to promote this transformation. PMID:27513164

  4. Lanthanide-Catalyzed Reversible Alkynyl Exchange by Carbon-Carbon Single-Bond Cleavage Assisted by a Secondary Amino Group.


    Shao, Yinlin; Zhang, Fangjun; Zhang, Jie; Zhou, Xigeng


    Lanthanide-catalyzed alkynyl exchange through C-C single-bond cleavage assisted by a secondary amino group is reported. A lanthanide amido complex is proposed as a key intermediate, which undergoes unprecedented reversible β-alkynyl elimination followed by alkynyl exchange and imine reinsertion. The in situ homo- and cross-dimerization of the liberated alkyne can serve as an additional driving force to shift the metathesis equilibrium to completion. This reaction is formally complementary to conventional alkyne metathesis and allows the selective transformation of internal propargylamines into those bearing different substituents on the alkyne terminus in moderate to excellent yields under operationally simple reaction conditions. PMID:27510403

  5. Structure sensitivity of hydrogenolytic cleavage of endocyclic and exocyclic C-C bonds in methylcyclohexane over supported iridium particles

    SciTech Connect

    Shi, Hui; Gutierrez, Oliver Y.; Haller, Gary L.; Mei, Donghai; Rousseau, Roger J.; Lercher, Johannes A.


    Structure sensitivities, H2 pressure effects and temperature dependencies for rates and selectivities of endo- and exocyclic C–C bond cleavage in methylcyclohexane were studied over supported Ir catalysts. The rate of endocyclic C–C bond cleavage first decreased and then increased with declining Ir dispersion from 0.65 to 0.035. The ring opening (RO) product distribution remained unchanged with varying H2 pressure on small Ir particles, while further shifting to methylhexanes with increasing H2 pressure on large particles. In contrast, the rate and selectivity of exocyclic C–C bond cleavage decreased monotonically with increasing H2 pressure and decreasing Ir particle size. The distinct dependencies of endocyclic and exocyclic C–C bond cleavage pathways on Ir dispersion and H2 pressure suggest that they are mediated by surface species with different ensemble size requirements. DFT calculations were performed on an Ir50 cluster and an Ir(111) surface, with or without pre-adsorbed hydrogen atoms, to provide insight into the observed effects of particle size and H2 pressure on RO pathways. On small Ir particles, the calculated dehydrogenation enthalpies for all endocyclic bonds were similar and affected to similar extents by H2 pressure; on large particles, the selectivity to n-heptane (via substituted C-C bond cleavage) was even lower than on small particles as a result of the least favorable adsorption and dehydrogenation energetics for hindered bonds. This work was supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences under Contract DE-AC05-76RL01830. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The computing time is provided by the user project from EMSL, a national scientific user facility sponsored by the US Department of Energy's Office of Biological and Environmental Research and located at Pacific

  6. Modern Transition-Metal-Catalyzed Carbon-Halogen Bond Formation.


    Petrone, David A; Ye, Juntao; Lautens, Mark


    The high utility of halogenated organic compounds has prompted the development of a vast number of transformations which install the carbon-halogen motif. Traditional routes to these building blocks have commonly involved multiple steps, harsh reaction conditions, and the use of stoichiometric and/or toxic reagents. In this regard, using transition metals to catalyze the synthesis of organohalides has become a mature field in itself, and applying these technologies has allowed for a decrease in the production of waste, higher levels of regio- and stereoselectivity, and the ability to produce enantioenriched target compounds. Furthermore, transition metals offer the distinct advantage of possessing a diverse spectrum of mechanistic possibilities which translate to the capability to apply new substrate classes and afford novel and difficult-to-access structures. This Review provides comprehensive coverage of modern transition metal-catalyzed syntheses of organohalides via a diverse array of mechanisms. Attention is given to the seminal stoichiometric organometallic studies which led to the corresponding catalytic processes being realized. By breaking this field down into the synthesis of aryl, vinyl, and alkyl halides, it becomes clear which methods have surfaced as most favored for each individual class. In general, a pronounced shift toward the use of C-H bonds as key functional groups, in addition to methods which proceed by catalytic, radical-based mechanisms has occurred. Although always evolving, this field appears to be heading in the direction of using starting materials with a significantly lower degree of prefunctionalization in addition to less expensive and abundant metal catalysts. PMID:27341176

  7. Formation of C-C bonds by mandelonitrile lyase in organic solvents.


    Wehtje, E; Adlercreutz, P; Mattiasson, B


    Mandelonitrile lyase (EC catalyzes the formation of D-mandelonitrile from HCN and benzaldehyde. Mandelonitrile lyase was immobilized by adsorption to support materials, for example, Celite. The enzyme preparations were used in diisopropyl ether for production of D-mandelonitrile. In order to obtain optically pure D-mandelonitrile it was necessary to use reaction conditions which favor the enzymatic reaction and suppress the competing spontaneous reaction, which yields a racemic mixture of D, L-mandelonitrile. The effects of substrate concentrations, water content, and support materials on both the spontaneous and enzymatic reactions were studied. The enzymatic reaction was carried out under conditions where the importance of the spontaneous reaction was negligible and high enantiomeric purity of D-mandelonitrile was achieved (at least 98% enantiomeric excess). The operational stability of the enzyme preparations was studied in batch as well as in continuous systems. It was vital to control the water content in the system to maintain an active preparation. In a packed bed reactor the enzyme preparations were shown to be active and stable. The reactors were run for 50 h with only a small decrease in product yield. PMID:18592607

  8. Cyanoalkylation: Alkylnitriles in Catalytic C-C Bond-Forming Reactions.


    López, Rosa; Palomo, Claudio


    Alkylnitriles are one of the most ubiquitous nitrogen-containing chemicals and are widely employed in reactions which result in nitrile-group conversion into other functionalities. Nevertheless, their use as carbon pronucleophiles in carbon-carbon bond-forming reactions has been hampered by difficulties associated mainly with the catalytic generation of active species, that is, α-cyano carbanions or metalated nitriles. Recent investigations have addressed this challenge and have resulted in different modes of alkylnitrile activation. This review illustrates these findings, which have set the foundation for the development of practical and conceptually new catalytic, direct cyanoalkylation methodologies. PMID:26387483

  9. Palladium-Catalyzed Intramolecular Carbene Insertion into C(sp(3) )-H Bonds.


    Solé, Daniel; Mariani, Francesco; Bennasar, M-Lluïsa; Fernández, Israel


    A palladium-catalyzed carbene insertion into C(sp(3) )-H bonds leading to pyrrolidines was developed. The coupling reaction can be catalyzed by both Pd(0) and Pd(II) , is regioselective, and shows a broad functional group tolerance. This reaction is the first example of palladium-catalyzed C(sp(3) )-C(sp(3) ) bond assembly starting from diazocarbonyl compounds. DFT calculations revealed that this direct C(sp(3) )-H bond functionalization reaction involves an unprecedented concerted metalation-deprotonation step. PMID:27079473

  10. CYP96T1 of Narcissus sp. aff. pseudonarcissus Catalyzes Formation of the Para-Para' C-C Phenol Couple in the Amaryllidaceae Alkaloids

    PubMed Central

    Kilgore, Matthew B.; Augustin, Megan M.; May, Gregory D.; Crow, John A.; Kutchan, Toni M.


    The Amaryllidaceae alkaloids are a family of amino acid derived alkaloids with many biological activities; examples include haemanthamine, haemanthidine, galanthamine, lycorine, and maritidine. Central to the biosynthesis of the majority of these alkaloids is a C-C phenol-coupling reaction that can have para-para', para-ortho', or ortho-para' regiospecificity. Through comparative transcriptomics of Narcissus sp. aff. pseudonarcissus, Galanthus sp., and Galanthus elwesii we have identified a para-para' C-C phenol coupling cytochrome P450, CYP96T1, capable of forming the products (10bR,4aS)-noroxomaritidine and (10bS,4aR)-noroxomaritidine from 4′-O-methylnorbelladine. CYP96T1 was also shown to catalyzed formation of the para-ortho' phenol coupled product, N-demethylnarwedine, as less than 1% of the total product. CYP96T1 co-expresses with the previously characterized norbelladine 4′-O-methyltransferase. The discovery of CYP96T1 is of special interest because it catalyzes the first major branch in Amaryllidaceae alkaloid biosynthesis. CYP96T1 is also the first phenol-coupling enzyme characterized from a monocot. PMID:26941773

  11. Pd-Catalyzed C-H Bond Functionalization on the Indole and Pyrrole Nucleus

    NASA Astrophysics Data System (ADS)

    Beck, Elizabeth M.; Gaunt, Matthew J.

    This review details recent developments in the Pd-catalyzed C-H bond arylation and alkenylation of indoles and pyrroles, aromatic heterocycles that are frequently displayed in natural products and medicinal agents.

  12. Iridium-Catalyzed Branch-Selective Hydroarylation of Vinyl Ethers via C-H Bond Activation.


    Ebe, Yusuke; Nishimura, Takahiro


    Iridium-catalyzed hydroarylation of vinyl ethers via a directed C-H bond activation of aromatic compounds gave high yields of the corresponding addition products with high branch selectivity. PMID:25928127

  13. Rhodium-Catalyzed ipso-Borylation of Alkylthioarenes via C-S Bond Cleavage.


    Uetake, Yuta; Niwa, Takashi; Hosoya, Takamitsu


    Rhodium-catalyzed transformation of alkyl aryl sulfides into arylboronic acid pinacol esters via C-S bond cleavage is reported. In combination with transition-metal-catalyzed sulfanyl group-guided regioselective C-H borylation reactions of alkylthioarenes, this method allows the synthesis of a diverse range of multisubstituted arenes. PMID:27210907

  14. C–H bond halogenation catalyzed or mediated by copper: an overview

    PubMed Central

    Hao, Wenyan


    Summary Carbon–halogen (C–X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C–X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C–X (X = F, Cl, Br, I) bond formation via direct C–H bond transformation is reviewed. PMID:26664634

  15. C-H bond halogenation catalyzed or mediated by copper: an overview.


    Hao, Wenyan; Liu, Yunyun


    Carbon-halogen (C-X) bonds are amongst the most fundamental groups in organic synthesis, they are frequently and widely employed in the synthesis of numerous organic products. The generation of a C-X bond, therefore, constitutes an issue of universal interest. Herein, the research advances on the copper-catalyzed and mediated C-X (X = F, Cl, Br, I) bond formation via direct C-H bond transformation is reviewed. PMID:26664634

  16. Transition-Metal-Catalyzed Redox-Neutral and Redox-Green C-H Bond Functionalization.


    Wang, Hongli; Huang, Hanmin


    Transition-metal-catalyzed C-H bond functionalization has become one of the most promising strategies to prepare complex molecules from simple precursors. However, the utilization of environmentally unfriendly oxidants in the oxidative C-H bond functionalization reactions reduces their potential applications in organic synthesis. This account describes our recent efforts in the development of a redox-neutral C-H bond functionalization strategy for direct addition of inert C-H bonds to unsaturated double bonds and a redox-green C-H bond functionalization strategy for realization of oxidative C-H functionalization with O2 as the sole oxidant, aiming to circumvent the problems posed by utilizing environmentally unfriendly oxidants. In principle, these redox-neutral and redox-green strategies pave the way for establishing new environmentally benign transition-metal-catalyzed C-H bond functionalization strategies. PMID:27258190

  17. Phenyltrimethylammonium Salts as Methylation Reagents in the Nickel-Catalyzed Methylation of C-H Bonds.


    Uemura, Takeshi; Yamaguchi, Mao; Chatani, Naoto


    Methylation of C(sp(2))-H bonds was achieved through the Ni(II)-catalyzed reaction of benzamides with phenyltrimethylammonium bromide or iodide as the source of the methyl group. The reaction has a broad scope and shows high functional-group compatibility. The reaction is also applicable to the methylation of C(sp(3))-H bonds in aliphatic amides. PMID:26821872

  18. Recent advances in the gold-catalyzed additions to C–C multiple bonds

    PubMed Central

    Huang, He; Zhou, Yu


    Summary C–O, C–N and C–C bonds are the most widespread types of bonds in nature, and are the cornerstone of most organic compounds, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. Cationic gold acts as a soft and carbophilic Lewis acid and is considered one of the most powerful activators of C–C multiple bonds. Consequently, gold-catalysis plays an important role in the development of new strategies to form these bonds in more convenient ways. In this review, we highlight recent advances in the gold-catalyzed chemistry of addition of X–H (X = O, N, C) bonds to C–C multiple bonds, tandem reactions, and asymmetric additions. This review covers gold-catalyzed organic reactions published from 2008 to the present. PMID:21804887

  19. Influence of sulfur addition and S-induced wall catalytic effect on C-C bond cleavage and aromatics hydrogenation

    SciTech Connect

    Schmidt, E.; Song, C.; Schobert, H.H.


    Catalytic hydrocracking of 4-(-1-naphthylmethyl)bibenzyl NMBB predominately yielded naphthalene and 4-methylbibenzyl. Sulfur addition to most catalyst precursors lead to substantially higher catalyst activity and subsequently higher conversion. In order to clarify the effect of sulfur alone on model compound conversion, NMBB was treated with sulfur in concentrations of 1.2 to 3.4 wt%, corresponding to conditions present in catalytic runs with sulfur. It was found that increasing sulfur concentrations leads to higher NMBB conversion. Furthermore, sulfur had a permanent influence on the reactor walls. It reacted with the transition metals in the steel to form a microscopic black iron sulfide layer on the surface, which could not be removed mechanically. The {open_quotes}non catalytic{close_quotes} runs after experiments with added sulfur yielded higher conversion than normal runs with new reactors. This {open_quotes}wall catalytic effect{close_quotes} can be reduced by treating sulfided reactors with hydrochloric acid for a short period of time and subsequent immersing into a base bath over night. These results demonstrate the significant influence of sulfur addition and S-induced residual wall-effect on C-C bond cleavage and hydrogenation of aromatics in batch reactors.

  20. Influence of sulfur addition and S-induced wall catalytic effects on C-C bond cleavage and aromatics hydrogenation

    SciTech Connect

    Schmidt, E.; Song, Chunshan; Schobert, H.H.


    Catalytic hydrocracking of 4-(1-naphthylmethyl)bibenzyl, designated as NMBB, predominately yielded naphthalene and 4-methylbibenzyl. Sulfur addition to most catalyst precursors lead to substantially higher catalyst activity and subsequently higher conversion. NMBB was also treated with sulfur alone in the absence of catalysts in concentrations of 1.2 to 3.4 wt, corresponding to conditions present in catalytic runs with added sulfur to precursors. It was found that increasing sulfur concentrations lead to higher NMBB conversion. Furthermore, sulfur had a permanent influence on the reactor walls. It reacted with the transition metals in the stainless steel to form a microscopic black iron sulfide layer on the surface, which could not be removed mechanically. The {open_quotes}non-catalytic{close_quotes} runs which were done after experiments with added sulfur yielded higher conversions than normal runs done in new reactors. This {open_quotes}wall catalytic effect{close_quotes} can be reduced by treating sulfided reactors with hydrochloric acid for a short period of time and subsequent immersing into a base bath overnight. These results demonstrate the significant influence of sulfur addition and S-induced residual wall-effect on C-C bond cleavage and hydrogenation of aromatics in batch reactors.

  1. C-H Bond activation and C-C bond formation in the reaction of 2,5-dimethylthiophene with TpMe2Ir compounds.


    Paneque, Margarita; Poveda, Manuel L; Carmona, Ernesto; Salazar, Verónica


    The bulky 2,5-dimethylthiophene (2,5-Me2T) reacts at 60 degrees C with TpMe2Ir(C2H4)2 to give a mixture of two TpMe2Ir(III) hydride products, 3 and 4, that contain in addition a thienyl (3) or a thienyl-derived ligand (4). For the generation of 3 only sp2 C-H activation is needed, but the formation of 4 requires also the activation of an sp3 C-H bond and the formation of a new C-C bond (between vinyl and thienyl fragments). In the presence of 2,5-Me2T, compound 4 reacts further to produce a complex thiophenic structure (5, characterized by X-ray methods) that derives formally from two molecules of 2,5-Me2T and a vinyl fragment. Compounds 3-5 can be readily protonated by [H(OEt2)2][BAr'4](Ar'= 3,5-C6H3(CF3)2), with initial generation of carbene ligands (in the case of 3 and 5) as a consequence of H+ attack at the beta-carbon of the Ir-thienyl unit. Free, substituted thiophenes, derived from the original 2,5-Me2T, may be isolated in this way. PMID:15824780

  2. A Substrate-Assisted Mechanism of Nucleophile Activation in a Ser-His-Asp Containing C-C Bond Hydrolase

    SciTech Connect

    Ruzzini, Antonio C.; Bhowmik, Shiva; Ghosh, Subhangi; Yam, Katherine C.; Bolin, Jeffrey T.; Eltis, Lindsay D.


    The meta-cleavage product (MCP) hydrolases utilize a Ser–His–Asp triad to hydrolyze a carbon–carbon bond. Hydrolysis of the MCP substrate has been proposed to proceed via an enol-to-keto tautomerization followed by a nucleophilic mechanism of catalysis. Ketonization involves an intermediate, ESred, which possesses a remarkable bathochromically shifted absorption spectrum. We investigated the catalytic mechanism of the MCP hydrolases using DxnB2 from Sphingomonas wittichii RW1. Pre-steady-state kinetic and LC ESI/MS evaluation of the DxnB2-mediated hydrolysis of 2-hydroxy-6-oxo-6-phenylhexa-2,4-dienoic acid to 2-hydroxy-2,4-pentadienoic acid and benzoate support a nucleophilic mechanism catalysis. In DxnB2, the rate of ESred decay and product formation showed a solvent kinetic isotope effect of 2.5, indicating that a proton transfer reaction, assigned here to substrate ketonization, limits the rate of acylation. For a series of substituted MCPs, this rate was linearly dependent on MCP pKa2nuc ~ 1). Structural characterization of DxnB2 S105A:MCP complexes revealed that the catalytic histidine is displaced upon substrate-binding. The results provide evidence for enzyme-catalyzed ketonization in which the catalytic His–Asp pair does not play an essential role. The data further suggest that ESred represents a dianionic intermediate that acts as a general base to activate the serine nucleophile. This substrate-assisted mechanism of nucleophilic catalysis distinguishes MCP hydrolases from other serine hydrolases.

  3. Stereoselective Halogenation of Integral Unsaturated C-C Bonds in Chemically and Mechanically Robust Zr and Hf MOFs.


    Marshall, Ross J; Griffin, Sarah L; Wilson, Claire; Forgan, Ross S


    Metal-organic frameworks (MOFs) containing Zr(IV) -based secondary building units (SBUs), as in the UiO-66 series, are receiving widespread research interest due to their enhanced chemical and mechanical stabilities. We report the synthesis and extensive characterisation, as both bulk microcrystalline and single crystal forms, of extended UiO-66 (Zr and Hf) series MOFs containing integral unsaturated alkene, alkyne and butadiyne units, which serve as reactive sites for postsynthetic modification (PSM) by halogenation. The water stability of a Zr-stilbene MOF allows the dual insertion of both -OH and -Br groups in a single, aqueous bromohydrination step. Quantitative bromination of alkyne- and butadiyne-containing MOFs is demonstrated to be stereoselective, as a consequence of the linker geometry when bound in the MOFs, while the inherent change in hybridisation and geometry of integral linker atoms is facilitated by the high mechanical stabilities of the MOFs, allowing bromination to be characterised in a single-crystal to single-crystal (SCSC) manner. The facile addition of bromine across the unsaturated C-C bonds in the MOFs in solution is extended to irreversible iodine sequestration in the vapour phase. A large-pore interpenetrated Zr MOF demonstrates an I2 storage capacity of 279 % w/w, through a combination of chemisorption and physisorption, which is comparable to the highest reported capacities of benchmark iodine storage materials for radioactive I2 sequestration. We expect this facile PSM process to not only allow trapping of toxic vapours, but also modulate the mechanical properties of the MOFs. PMID:26916707

  4. A facile C-C bond cleavage in the epoxides and its use for the synthesis of oxygenated heterocycles by a ring expansion strategy.


    Lakshmipathi, Pandarinathan; Grée, Danielle; Grée, René


    The bicyclic epoxy alcohols when treated with DAST gave a new class of rearranged organofluorine compounds, by a ring expansion via C-C bond cleavage of the oxirane ring. The outcome of this reaction with respect to ring size and stereochemical relation between the functionalities is presented here. PMID:11820902

  5. Copper-catalyzed etherification of arene C-H bonds.


    Roane, James; Daugulis, Olafs


    A method for direct, auxiliary-assisted alkoxylation and phenoxylation of β-sp(2) C-H bonds of benzoic acid derivatives and γ-sp(2) C-H bonds of amine derivatives is reported. The reaction employs (CuOH)2CO3 catalyst, air as an oxidant, phenol or alcohol coupling partner, DMF, pyridine, or DMPU solvent, and K2CO3, tetramethylguanidine, or K3PO4 base at 70-130 °C. PMID:24180517

  6. Ester-directed Ru-catalyzed C-O activation/C-C coupling reaction of ortho-methoxy naphthoates with organoboroneopentylates.


    Zhao, Yigang; Snieckus, Victor


    A new, catalytic and general synthetic methodology for the construction of biaryls and heterobiaryls by the cross-coupling of ortho-methoxy naphthoates with organoboroneopentylates is disclosed. The reaction proceeds under RuH2(CO)(PPh3)3-catalyzed conditions driven by unreactive C-O bond activation of a proximate ester directing group (DG)-catalyst chelation. This one-step synthesis of 2-aryl and -heteroaryl-1-naphthoates has the features of operational simplicity, minimum waste and convenient scale-up. The hierarchy of C(O)Me > CONEt2 > CO2Me coordination-assisted reactivity, of potential value in chemoselective synthesis, is also established. PMID:26661919

  7. Copper(I)-catalyzed alkylation of polyfluoroarenes through Direct C-H bond functionalization.


    Xu, Shuai; Wu, Guojiao; Ye, Fei; Wang, Xi; Li, Huan; Zhao, Xia; Zhang, Yan; Wang, Jianbo


    The copper(I)-catalyzed alkylation of electron-deficient polyfluoroarenes with N-tosylhydrazones and diazo compounds has been developed. This reaction uses readily available starting materials and is operationally simple, thus representing a practical method for the construction of C(sp(2) )-C(sp(3) ) bonds with polyfluoroarenes through direct C-H bond functionalization. Mechanistically, copper(I) carbene formation and subsequent migratory insertion are proposed as the key steps in the reaction pathway. PMID:25690761

  8. Synthesis of sulfonamides via copper-catalyzed oxidative C-N bond cleavage of tertiary amines.


    Ji, Jing; Liu, Zhengyi; Liu, Ping; Sun, Peipei


    A copper-catalyzed coupling reaction of sulfonyl chlorides with tertiary amines via the oxidative C-N bond cleavage of tertiary amines was developed. Sulfonamides were synthesized using this strategy in moderate to good yields. The reaction was applicable to various tertiary amines, as well as sulfonyl chlorides. PMID:27356858

  9. Cobalt(III)-Catalyzed C–H Bond Amidation with Isocyanates

    PubMed Central

    Hummel, Joshua R.; Ellman, Jonathan A.


    The first examples of cobalt(III)-catalyzed C–H bond addition to isocyanates are described, providing a convergent strategy for arene and heteroarene amidation. Using a robust air- and moisture-stable catalyst, this transformation demonstrates broad isocyanate scope, good functional-group compatibility and has been performed on gram scale. PMID:25945401

  10. Direct 2-acetoxylation of quinoline N-oxides via copper catalyzed C-H bond activation.


    Chen, Xuan; Zhu, Chongwei; Cui, Xiuling; Wu, Yangjie


    An efficient and direct 2-acetoxylation of quinoline N-oxides via copper(I) catalyzed C-H bond activation has been developed. This transformation was achieved using TBHP as an oxidant in the cross-dehydrogenative coupling (CDC) reaction of quinoline N-oxides with aldehydes, and provided a practical pathway to 2-acyloxyl quinolines. PMID:23793162

  11. Nickel-Catalyzed Intramolecular C-O Bond Formation: Synthesis of Cyclic Enol Ethers.


    Han, Seo-Jung; Doi, Ryohei; Stoltz, Brian M


    An efficient and exceptionally mild intramolecular nickel-catalyzed carbon-oxygen bond-forming reaction between vinyl halides and primary, secondary, and tertiary alcohols has been achieved. Zinc powder was found to be an essential additive for obtaining high catalyst turnover and yields. This operationally simple method allows direct access to cyclic vinyl ethers in high yields in a single step. PMID:27159831

  12. Identification of Possible Pathways for C-C Bond Formation during Electrochemical Reduction of CO2: New Theoretical Insights from an Improved Electrochemical Model.


    Goodpaster, Jason D; Bell, Alexis T; Head-Gordon, Martin


    We have carried out a periodic Kohn-Sham density functional theory investigation of the pathways by which carbon-carbon bonds could be formed during the electrochemical reduction of CO2 on Cu(100) using a model that includes the effects of the electrochemical potential, solvent, and electrolyte. The electrochemical potential was set by relating the applied potential to the Fermi energy and then calculating the number of electrons required by the simulation cell for that specific Fermi energy. The solvent was included as a continuum dielectric, and the electrolyte was described using a linearized Poisson-Boltzmann model. The calculated potential of zero charge for a variety of surfaces agrees with experiment to within a mean average error of 0.09 V, thereby validating the assumptions of the model. Analysis of the mechanism for C-C bond formation revealed that at low-applied potential, C-C bond formation occurs through a CO dimer. However, at high applied potentials, a large activation barrier blocks this pathway; therefore, C-C bond formation occurs through reaction of adsorbed CHO and CO. Rate parameters determined from our calculations were used to simulate the kinetics of ethene formation during the electrochemical reduction of CO over a Cu(100) surface. An excellent match was observed between previously reported measurements of the partial current for ethene formation as a function of applied voltage and the variation in the partial current for C-C bond formation predicted by our microkinetic model. The electrochemical model reported here is simple, fairly easy to implement, and involves only a small increase in computational cost over calculations neglecting the effects of the electrolyte and the applied field. Therefore, it can be used to study the effects of applied potential and electrolyte composition on the energetics of surface reactions for a wide variety of electrochemical reactions. PMID:27045040

  13. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.


    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning


    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process. PMID:25251943

  14. Catalytic constructive deoxygenation of lignin-derived phenols: new C-C bond formation processes from imidazole-sulfonates and ether cleavage reactions.


    Leckie, Stuart M; Harkness, Gavin J; Clarke, Matthew L


    As part of a programme aimed at exploiting lignin as a chemical feedstock for less oxygenated fine chemicals, several catalytic C-C bond forming reactions utilising guaiacol imidazole sulfonate are demonstrated. These include the cross-coupling of a Grignard, a non-toxic cyanide source, a benzoxazole, and nitromethane. A modified Meyers reaction is used to accomplish a second constructive deoxygenation on a benzoxazole functionalised anisole. PMID:25130565

  15. HC[triple bond]P and H3C-C[triple bond]P as proton acceptors in protonated complexes containing two phosphorus bases: structures, binding energies, and spin-spin coupling constants.


    Alkorta, Ibon; Elguero, José; Bene, Janet E Del


    Ab initio calculations at the MP2/aug'-cc-pVTZ level have been carried out to investigate the structures and binding energies of cationic complexes involving protonated sp, sp2, and sp3 phosphorus bases as proton donor ions and the sp-hybridized phosphorus bases H-C[triple bond]P and H3C-C[triple bond]P as proton acceptors. These proton-bound complexes exhibit a variety of structural motifs, but all are stabilized by interactions that occur through the pi cloud of the acceptor base. The binding energies of these complexes range from 6 to 15 kcal/mol. Corresponding complexes with H3C-C[triple bond]P as the proton acceptor are more stable than those with H-C[triple bond]P as the acceptor, a reflection of the greater basicity of H3C-C[triple bond]P. In most complexes with sp2- or sp3-hybridized P-H donor ions, the P-H bond lengthens and the P-H stretching frequency is red-shifted relative to the corresponding monomers. Complex formation also leads to a lengthening of the C[triple bond]P bond and a red shift of the C[triple bond]P stretching vibration. The two-bond coupling constants 2pihJ(P-P) and 2pihJ(P-C) are significantly smaller than 2hJ(P-P) and 2hJ(P-C) for complexes in which hydrogen bonding occurs through lone pairs of electrons on P or C. This reflects the absence of significant s electron density in the hydrogen-bonding regions of these pi complexes. PMID:17760429

  16. Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene.


    Yang, X X; Li, J W; Zhou, Z F; Wang, Y; Yang, L W; Zheng, W T; Sun, Chang Q


    From the perspective of bond relaxation and bond vibration, we have formulated the Raman phonon relaxation of graphene, under the stimuli of the number-of-layers, the uni-axial strain, the pressure, and the temperature, in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of the Raman shifts, which are due to the number-of-layers reduction, of the G-peak shift and arises from the vibration of a pair of atoms, while the D- and the 2D-peak shifts involve the z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C(3v) bond geometry to the C(2v) uni-axial bond elongation; (iii) the thermal softening of the phonons originates from bond expansion and weakening; and (iv) the pressure stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift as well as the length, energy, force constant, Debye temperature, compressibility and elastic modulus of the C-C bond in graphene, which is of instrumental importance in the understanding of the unusual behavior of graphene. PMID:22105904

  17. Gold-Catalyzed Synthesis of Heterocycles

    NASA Astrophysics Data System (ADS)

    Arcadi, Antonio


    The following sections are included: * Introduction * Synthesis of Heterocycles via Gold-Catalyzed Heteroatom Addition to Unsaturated C-C Bonds * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cyclization of Polyunsaturated Compounds * Synthesis of Heterocyclic Compounds via α-Oxo Gold Carbenoid * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Cycloaddition Reactions * Synthesis of Heterocyclic Derivatives through Gold-Catalyzed Activation of Carbonyl Groups and Alcohols * Synthesis of Heterocyclic Compounds through Gold-Mediated C-H Bond Functionalization * Gold-Catalyzed Domino Cyclization/Oxidative Coupling Reactions * Conclusions * References

  18. Formation of C–C bonds via ruthenium-catalyzed transfer hydrogenation*

    PubMed Central

    Moran, Joseph; Krische, Michael J.


    Ruthenium-catalyzed transfer hydrogenation of diverse π-unsaturated reactants in the presence of aldehydes provides products of carbonyl addition. Dehydrogenation of primary alcohols in the presence of the same π-unsaturated reactants provides identical products of carbonyl addition. In this way, carbonyl addition is achieved from the alcohol or aldehyde oxidation level in the absence of stoichiometric organometallic reagents or metallic reductants. In this account, the discovery of ruthenium-catalyzed C–C bond-forming transfer hydrogenations and the recent development of diastereo- and enantioselective variants are discussed. PMID:23430602

  19. Selectfluor-Mediated Simultaneous Cleavage of C-O and C-C Bonds in α,β-Epoxy Ketones Under Transition-Metal-Free Conditions: A Route to 1,2-Diketones.


    Wang, Heng; Ren, Shaobo; Zhang, Jian; Zhang, Wei; Liu, Yunkui


    Selectfluor-mediated simultaneous cleavage of C-O and C-C bonds in α,β-epoxy ketones has been successfully achieved under transition-metal-free conditions. The reaction gives 1,2-diketone compounds in moderate to good yields involving a ring-opening/benzoyl rearrangement/C-C bond cleavage sequence under oxidative conditions. PMID:26050519

  20. Manganese Porphyrins Catalyze Selective C-H Bond Halogenations

    SciTech Connect

    Liu, Wei; Groves, John T.


    We report a manganese porphyrin mediated aliphatic C-H bond chlorination using sodium hypochlorite as the chlorine source. In the presence of catalytic amounts of phase transfer catalyst and manganese porphyrin Mn(TPP)Cl 1, reaction of sodium hypochlorite with different unactivated alkanes afforded alkyl chlorides as the major products with only trace amounts of oxygenation products. Substrates with strong C-H bonds, such as neopentane (BDE =~100 kcal/mol) can be also chlorinated with moderate yield. Chlorination of a diagnostic substrate, norcarane, afforded rearranged products indicating a long-lived carbon radical intermediate. Moreover, regioselective chlorination was achieved by using a hindered catalyst, Mn(TMP)Cl, 2. Chlorination of trans-decalin with 2 provided 95% selectivity for methylene-chlorinated products as well as a preference for the C2 position. This novel chlorination system was also applied to complex substrates. With 5α-cholestane as the substrate, we observed chlorination only at the C2 and C3 positions in a net 55% yield, corresponding to the least sterically hindered methylene positions in the A-ring. Similarly, chlorination of sclareolide afforded the equatorial C2 chloride in a 42% isolated yield. Regarding the mechanism, reaction of sodium hypochlorite with the MnIII porphyrin is expected to afford a reactive MnV=O complex that abstracts a hydrogen atom from the substrate, resulting in a free alkyl radical and a MnIV—OH complex. We suggest that this carbon radical then reacts with a MnIV—OCl species, providing the alkyl chloride and regenerating the reactive MnV=O complex. The regioselectivity and the preference for CH2 groups can be attributed to nonbonded interactions between the alkyl groups on the substrates and the aryl groups of the manganese porphyrin. The results are indicative of a bent [Mnv=O---H---C] geometry due to the C—H approach to the Mn

  1. C-C Bond Formation via Copper-Catalyzed Conjugate Addition Reactions to Enones in Water at Room Temperature

    PubMed Central

    Lipshutz, Bruce H.; Huang, Shenlin; Leong, Wendy Wen Yi; Isley, Nicholas A.


    Conjugate addition reactions to enones can now be done in water at room temperature with in situ-generated organocopper reagents. Mixing an enone, zinc powder, TMEDA, and an alkyl halide in a micellar environemnt containing catalytic amounts of Cu(I), Ag(I), and Au(III), leads to 1,4-adducts in good isolated yields: no organometallic precursor is involved. PMID:23190029

  2. Theoretical insights into how the first C-C bond forms in the methanol-to-olefin process catalysed by HSAPO-34.


    Peng, Chao; Wang, Haifeng; Hu, P


    We report here a comprehensive understanding of the first C-C coupling during the induction period of the methanol-to-olefin process using density functional theory with the HSE06 hybrid functional. We illustrate the possible routes of formation for the active carbenium ion (CH3OCH2(+)), which has been identified to play an important part in triggering the formation of the first C-C bond and the hydrocarbon pool species. CH3OCH2(+) can be generated not only from dimethyl ether and Z(O)-CH3, but also from the reaction of HCHO and Z(O)-CH3, which has a lower effective barrier. An understanding of the dominance of CH3OCH2(+) over other carbocations and direct C-C coupling pathways is presented and quantitatively analysed. The charge distribution in the formation of CH3OCH2(+) is revealed and it is confirmed that the carbenium ion is thermodynamically more favoured than the radical. The subsequent reaction after the first C-C coupling was investigated, which uncovered some important active C2 species that possibly led to the formation of the active hydrocarbon pool intermediates and may finally realize the catalytic cycle. PMID:27173579

  3. Silver-catalyzed formal insertion of arynes into Rf-I bonds.


    Zeng, Yuwen; Hu, Jinbo


    An unprecedented silver-catalyzed formal insertion of arynes into Rf-I (Rf = CF3, C2F5) bonds has been developed. This protocol provides easy access to various ortho-perfluoroalkyl iodoarenes under mild conditions. In this insertion reaction, an ionic atom-transfer reaction of RfI occurs, and a silver-mediated metathesis process is involved in the efficient transfer of the electropositive iodine atom. PMID:24782445

  4. Recent advances in copper-catalyzed C-H bond amidation.


    Wan, Jie-Ping; Jing, Yanfeng


    Copper catalysis has been known as a powerful tool for its ubiquitous application in organic synthesis. One of the fundamental utilities of copper catalysis is in the C-N bond formation by using carbon sources and nitrogen functional groups such as amides. In this review, the recent progress in the amidation reactions employing copper-catalyzed C-H amidation is summarized. PMID:26664644

  5. Recent advances in copper-catalyzed C–H bond amidation

    PubMed Central

    Jing, Yanfeng


    Summary Copper catalysis has been known as a powerful tool for its ubiquitous application in organic synthesis. One of the fundamental utilities of copper catalysis is in the C–N bond formation by using carbon sources and nitrogen functional groups such as amides. In this review, the recent progress in the amidation reactions employing copper-catalyzed C–H amidation is summarized. PMID:26664644

  6. Cp*Co(III) -Catalyzed C(sp(3) )-H Bond Amidation of 8-Methylquinoline.


    Barsu, Nagaraju; Rahman, Md Atiur; Sen, Malay; Sundararaju, Basker


    An efficient and external oxidant-free, Cp*Co(III) -catalyzed C(sp(3) )-H bond amidation of 8-methylquinoline, using oxazolone as an efficient amidating agent, is reported for the first time under mild conditions. The reaction is selective and tolerates a variety of functional groups. Based on previous reports and experimental results, the deprotonation pathway proceeds through an external base-assisted concerted metalation and deprotonation process. PMID:27168249

  7. Transition-Metal-Catalyzed Laboratory-Scale Carbon–Carbon Bond-Forming Reactions of Ethylene

    PubMed Central

    Saini, Vaneet; Stokes, Benjamin J.; Sigman, Matthew S.


    Ethylene, the simplest alkene, is the most abundantly synthesized organic molecule by volume. It is readily incorporated into transitionmetal–catalyzed carbon-carbon bond-forming reactions through migratory insertions into alkylmetal intermediates. Because of its D2h symmetry, only one insertion outcome is possible. This limits byproduct formation and greatly simplifies analysis. As described within this Minireview, many carbon–carbon bond-forming reactions incorporate a molecule (or more) of ethylene at ambient pressure and temperature. In many cases, a useful substituted alkene is incorporated into the product. PMID:24105881

  8. Bonding and Integration of C-C Composite to Cu-Clad-Molybdenum for Thermal Management Applications

    NASA Technical Reports Server (NTRS)

    Asthana, R.; Singh, M.; Shpargel, T.P.


    Two- and three-dimensional carbon-carbon composites with either resin-derived matrix or CVI matrix were joined to Cu-clad-Mo using active Ag-Cu braze alloys for thermal management applications. The joint microstructure and composition were examined using Field-Emission Scanning Electron Microscopy and Energy-Dispersive Spectroscopy, and the joint hardness was characterized using the Knoop microhardness testing. Observations on the infiltration of the composite with molten braze, dissolution of metal substrate, and solute segregation at the C-C surface have been discussed. The thermal response of the integrated assembly is also briefly discussed.

  9. Active Metal Brazing and Adhesive Bonding of Titanium to C/C Composites for Heat Rejection System

    NASA Technical Reports Server (NTRS)

    Singh, M.; Shpargel, Tarah; Cerny, Jennifer


    Robust assembly and integration technologies are critically needed for the manufacturing of heat rejection system (HRS) components for current and future space exploration missions. Active metal brazing and adhesive bonding technologies are being assessed for the bonding of titanium to high conductivity Carbon-Carbon composite sub components in various shapes and sizes. Currently a number of different silver and copper based active metal brazes and adhesive compositions are being evaluated. The joint microstructures were examined using optical microscopy, and scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). Several mechanical tests have been employed to ascertain the effectiveness of different brazing and adhesive approaches in tension and in shear that are both simple and representative of the actual system and relatively straightforward in analysis. The results of these mechanical tests along with the fractographic analysis will be discussed. In addition, advantages, technical issues and concerns in using different bonding approaches will also be presented.

  10. Labile Cu(I) catalyst/spectator Cu(II) species in copper-catalyzed C-C coupling reaction: operando IR, in situ XANES/EXAFS evidence and kinetic investigations.


    He, Chuan; Zhang, Guanghui; Ke, Jie; Zhang, Heng; Miller, Jeffrey T; Kropf, Arthur J; Lei, Aiwen


    Insights toward the Cu-catalyzed C-C coupling reaction were investigated through operando IR and in situ X-ray absorption near-edge structure/extended X-ray absorption fine structure. It was found that the Cu(I) complex formed from the reaction of CuI with β-diketone nucleophile was liable under the cross-coupling conditions, which is usually considered as active catalytic species. This labile Cu(I) complex could rapidly disproportionate to the spectator Cu(II) and Cu(0) species under the reaction conditions, which was an off-cycle process. In this copper-catalyzed C-C coupling reaction, β-diketone might act both as the substrate and the ligand. PMID:23214954

  11. Efficient C-C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects.


    Loukrakpam, Rameshwori; Yuan, Qiuyi; Petkov, Valeri; Gan, Lin; Rudi, Stefan; Yang, Ruizhi; Huang, Yunhui; Brankovic, Stanko R; Strasser, Peter


    Efficient catalytic C-C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2 is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2 at very low electrode potentials owing to efficient C-C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt-Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis, in situ electrochemical FTIR spectroscopy, and in situ scanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity. PMID:25081353

  12. Synthesis of seco-B-ring bryostatin analogue WN-1 via C-C bond-forming hydrogenation: critical contribution of the B-ring in determining bryostatin-like and phorbol 12-myristate 13-acetate-like properties.


    Andrews, Ian P; Ketcham, John M; Blumberg, Peter M; Kedei, Noemi; Lewin, Nancy E; Peach, Megan L; Krische, Michael J


    The seco-B-ring bryostatin analogue, macrodiolide WN-1, was prepared in 17 steps (longest linear sequence) and 30 total steps with three bonds formed via hydrogen-mediated C-C coupling. This synthetic route features a palladium-catalyzed alkoxycarbonylation of a C2-symmetric diol to form the C9-deoxygenated bryostatin A-ring. WN-1 binds to PKCα (Ki = 16.1 nM) and inhibits the growth of multiple leukemia cell lines. Although structural features of the WN-1 A-ring and C-ring are shared by analogues that display bryostatin-like behavior, WN-1 displays PMA-like behavior in U937 cell attachment and proliferation assays, as well as in K562 and MV-4-11 proliferation assays. Molecular modeling studies suggest the pattern of internal hydrogen bonds evident in bryostatin 1 is preserved in WN-1, and that upon docking WN-1 into the crystal structure of the C1b domain of PKCδ, the binding mode of bryostatin 1 is reproduced. The collective data emphasize the critical contribution of the B-ring to the function of the upper portion of the molecule in conferring a bryostatin-like pattern of biological activity. PMID:25207655

  13. 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

    SciTech Connect

    Horsman, Geoff P.; Bhowmik, Shiva; Seah, Stephen Y.K.; Kumar, Pravindra; Bolin, Jeffrey T.; Eltis, Lindsay D.


    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., 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.

  14. Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

    SciTech Connect

    T. Brent Gunnoe


    Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials. A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt

  15. Toluene derivatives as simple coupling precursors for cascade palladium-catalyzed oxidative C-H bond acylation of acetanilides.


    Wu, Yinuo; Choy, Pui Ying; Mao, Fei; Kwong, Fuk Yee


    A palladium-catalyzed cascade cross-coupling of acetanilide and toluene for the synthesis of ortho-acylacetanilide is described. Toluene derivatives can act as effective acyl precursors (upon sp(3)-C-H bond oxidation by a Pd/TBHP system) in the oxidative coupling between two C-H bonds. This dehydrogenative Pd-catalyzed ortho-acylation proceeds under mild reaction conditions. PMID:23230572

  16. Stability of the C-C covalent bonds in fullerenes in the solid body-vapor structure during the thermodynamic action by a quasi-pulsed electron beam

    NASA Astrophysics Data System (ADS)

    Semenov, A. P.; Semenova, I. A.; Churilov, G. N.


    The explosive evaporation of a fullerene mixture in a vacuum of ˜10-2 Pa during the contraction of a 1-kW hollow electron beam into a spot on a substrate in a time of 0.1-1 s is considered. A comparative analysis of the Raman spectra and the absorption electron spectra of a starting fullerene mixture powder and the vapor condensates shows that the evaporation of C60 and C70 fullerenes proceeds without breaking C-C covalent bonds.

  17. Unique properties of C,C'-linked nido-biscarborane tetraanions. Synthesis, structure and bonding of ruthenium monocarbollide via unprecedented cage carbon extrusion.


    Zhao, Da; Zhang, Jiji; Lin, Zhenyang; Xie, Zuowei


    Four reaction pathways have been found in the reaction of a C,C'-linked nido-biscarborane tetraanionic salt with [Ru(p-cymene)Cl2]2, leading to the isolation and structural characterization of redox, triple cage B-H oxidative addition, cage expansion and cage carbon extrusion products. Among these, the unprecedented cage carbon extrusion results in the formation of a new 6π-electron carboranyl ligand [C2B10H10](2-). The bonding interactions between this ligand and the Ru(ii) center have also been discussed on the basis of DFT calculations. PMID:27405999

  18. C-C Bond Formation: Synthesis of C5 Substituted Pyrimidine and C8 Substituted Purine Nucleosides Using Water Soluble Pd-imidate Complex.


    Gayakhe, Vijay; Ardhapure, Ajaykumar V; Kapdi, Anant R; Sanghvi, Yogesh S; Serrano, Jose Luis; Schulzke, Carola


    The synthesis of a highly efficient, water soluble [Pd(Sacc)2 (TPA)2 ] complex for C-C bond formation is described. Additionally, application of the [Pd(Sacc)2 (TPA)2 ] complex for Suzuki-Miyaura arylation of all four nucleosides (5-iodo-2'-deoxyuridine [5-IdU], 5-iodo-2'-deoxycytidine [5-IdC], 8-bromo-2'-deoxyadenosine, and 8-bromo-2'-deoxyguanosine) with various aryl/heteroaryl boronic acids in plain water under milder conditions is demonstrated. © 2016 by John Wiley & Sons, Inc. PMID:27248782

  19. Iron-promoted C-C bond cleavage of 1,3-diketones: a route to 1,2-diketones under mild reaction conditions.


    Huang, Lehao; Cheng, Kai; Yao, Bangben; Xie, Yongju; Zhang, Yuhong


    A conceptual method for the preparation of 1,2-diketones is reported. The selective C-C bond cleavage of 1,3-diketones affords the 1,2-diketones in high yields under mild reaction conditions in air by the use of FeCl(3) as the catalyst and tert-butyl nitrite (TBN) as the oxidant without the use of solvent. The possible reaction mechanism is discussed. This protocol provides an expeditious route to the useful 1,2-diketones. PMID:21627329

  20. A free-standing condensation enzyme catalyzing ester bond formation in C-1027 biosynthesis.


    Lin, Shuangjun; Van Lanen, Steven G; Shen, Ben


    Nonribosomal peptide synthetases (NRPSs) catalyze the biosynthesis of many biologically active peptides and typically are modular, with each extension module minimally consisting of a condensation, an adenylation, and a peptidyl carrier protein domain responsible for incorporation of an amino acid into the growing peptide chain. C-1027 is a chromoprotein antitumor antibiotic whose enediyne chromophore consists of an enediyne core, a deoxy aminosugar, a benzoxazolinate, and a beta-amino acid moiety. Bioinformatics analysis suggested that the activation and incorporation of the beta-amino acid moiety into C-1027 follows an NRPS mechanism whereby biosynthetic intermediates are tethered to the peptidyl carrier protein SgcC2. Here, we report the biochemical characterization of SgcC5, an NRPS condensation enzyme that catalyzes ester bond formation between the SgcC2-tethered (S)-3-chloro-5-hydroxy-beta-tyrosine and (R)-1-phenyl-1,2-ethanediol, a mimic of the enediyne core. SgcC5 uses (S)-3-chloro-5-hydroxy-beta-tyrosyl-SgcC2 as the donor substrate and exhibits regiospecificity for the C-2 hydroxyl group of the enediyne core mimic as the acceptor substrate. Remarkably, SgcC5 is also capable of catalyzing amide bond formation, albeit with significantly reduced efficiency, between (S)-3-chloro-5-hydroxy-beta-tyrosyl-(S)-SgcC2 and (R)-2-amino-1-phenyl-1-ethanol, an alternative enediyne core mimic bearing an amine at its C-2 position. Thus, SgcC5 is capable of catalyzing both ester and amide bond formation, providing an evolutionary link between amide- and ester-forming condensation enzymes. PMID:19246381

  1. Synthesis of Indolizines through Oxidative Linkage of C-C and C-N Bonds from 2-Pyridylacetates.


    Mohan, Darapaneni Chandra; Ravi, Chitrakar; Pappula, Venkatanarayana; Adimurthy, Subbarayappa


    Synthesis of indolizine-1-carboxylates through the Ortoleva-King reaction of 2-pyridylacetate followed by the Aldol condensation under mild reaction conditions has been described. This protocol is compatible with a broad range of functional groups, and it has been also successfully extended to unsaturated ketones, bringing about the regioselective formation of benzoyl-substituted indolizines through Michael addition followed by C-N bond formation, which are difficult to prepare by previous methods in a single step. PMID:26044904

  2. Palladium- and Copper-Catalyzed Arylation of Carbon-Hydrogen Bonds

    PubMed Central

    Daugulis, Olafs; Do, Hien-Quang; Shabashov, Dmitry


    The transition-metal-catalyzed functionalization of C-H bonds is a powerful method for generating carbon-carbon bonds. Although significant advances to this field have been reported during the last decade, many challenges remain. First, most of the methods are substrate-specific and thus cannot be generalized. Second, conversions of unactivated (i.e. not benzylic or alpha to heteroatom) sp3 C–H bonds to C–C bonds are rare, with most examples limited to t-butyl groups—a conversion that is inherently simple because there are no β-hydrogens that can be eliminated. Finally, the palladium, rhodium, and ruthenium catalysts routinely used for the conversion of C–H bonds to C–C bonds are expensive. Catalytically active metals that are cheaper and less exotic (e.g. copper, iron, and manganese) are rarely used. This Account describes our attempts to provide solutions to these three problems. We have developed a general method for directing-group-containing arene arylation by aryl iodides. Using palladium acetate as the catalyst, we arylated anilides, benzamides, benzoic acids, benzylamines, and 2-substituted pyridine derivatives under nearly identical conditions. We have also developed a method for the palladium-catalyzed auxiliary-assisted arylation of unactivated sp3 C–H bonds. This procedure allows for the β-arylation of carboxylic acid derivatives and the γ-arylation of amine derivatives. Furthermore, copper catalysis can be used to mediate the arylation of acidic arene C–H bonds (i.e. those with pKa values <35 in DMSO). Using a copper iodide catalyst in combination with a base and a phenanthroline ligand, we successfully arylated electron-rich and electron-deficient heterocycles and electron-poor arenes possessing at least two electron-withdrawing groups. The reaction exhibits unusual regioselectivity: arylation occurs at the most hindered position. This copper-catalyzed method supplements the well-known C–H activation/borylation methodology, in which

  3. Palladium-catalyzed picolinamide-directed iodination of remote ortho-C-H bonds of arenes: Synthesis of tetrahydroquinolines.


    Nack, William A; Wang, Xinmou; Wang, Bo; He, Gang; Chen, Gong


    A new palladium-catalyzed picolinamide (PA)-directed ortho-iodination reaction of ε-C(sp(2))-H bonds of γ-arylpropylamine substrates is reported. This reaction proceeds selectively with a variety of γ-arylpropylamines bearing strongly electron-donating or withdrawing substituents, complementing our previously reported PA-directed electrophilic aromatic substitution approach to this transformation. As demonstrated herein, a three step sequence of Pd-catalyzed γ-C(sp(3))-H arylation, Pd-catalyzed ε-C(sp(2))-H iodination, and Cu-catalyzed C-N cyclization enables a streamlined synthesis of tetrahydroquinolines bearing diverse substitution patterns. PMID:27559375

  4. A Novel Strategy for Biomass Upgrade: Cascade Approach to the Synthesis of Useful Compounds via C-C Bond Formation Using Biomass-Derived Sugars as Carbon Nucleophiles.


    Yamaguchi, Sho; Baba, Toshihide


    Due to the depletion of fossil fuels, biomass-derived sugars have attracted increasing attention in recent years as an alternative carbon source. Although significant advances have been reported in the development of catalysts for the conversion of carbohydrates into key chemicals (e.g., degradation approaches based on the dehydration of hydroxyl groups or cleavage of C-C bonds via retro-aldol reactions), only a limited range of products can be obtained through such processes. Thus, the development of a novel and efficient strategy targeted towards the preparation of a range of compounds from biomass-derived sugars is required. We herein describe the highly-selective cascade syntheses of a range of useful compounds using biomass-derived sugars as carbon nucleophiles. We focus on the upgrade of C2 and C3 oxygenates generated from glucose to yield useful compounds via C-C bond formation. The establishment of this novel synthetic methodology to generate valuable chemical products from monosaccharides and their decomposed oxygenated materials renders carbohydrates a potential alternative carbon resource to fossil fuels. PMID:27447603

  5. Reactivity of biomimetic iron(II)-2-aminophenolate complexes toward dioxygen: mechanistic investigations on the oxidative C-C bond cleavage of substituted 2-aminophenols.


    Chakraborty, Biswarup; Bhunya, Sourav; Paul, Ankan; Paine, Tapan Kanti


    The isolation and characterization of a series of iron(II)-2-aminophenolate complexes [(6-Me3-TPA)Fe(II)(X)](+) (X = 2-amino-4-nitrophenolate (4-NO2-HAP), 1; X = 2-aminophenolate (2-HAP), 2; X = 2-amino-3-methylphenolate (3-Me-HAP), 3; X = 2-amino-4-methylphenolate (4-Me-HAP), 4; X = 2-amino-5-methylphenolate (5-Me-HAP), 5; X = 2-amino-4-tert-butylphenolate (4-(t)Bu-HAP), 6 and X = 2-amino-4,6-di-tert-butylphenolate (4,6-di-(t)Bu-HAP), 7) and an iron(III)-2-amidophenolate complex [(6-Me3-TPA)Fe(III)(4,6-di-(t)Bu-AP)](+) (7(Ox)) supported by a tripodal nitrogen ligand (6-Me3-TPA = tris(6-methyl-2-pyridylmethyl)amine) are reported. Substituted 2-aminophenols were used to prepare the biomimetic iron(II) complexes to understand the effect of electronic and structural properties of aminophenolate rings on the dioxygen reactivity and on the selectivity of C-C bond cleavage reactions. Crystal structures of the cationic parts of 5·ClO4 and 7·BPh4 show six-coordinate iron(II) centers ligated by a neutral tetradentate ligand and a monoanionic 2-aminophenolate in a bidentate fashion. While 1·BPh4 does not react with oxygen, other complexes undergo oxidative transformation in the presence of dioxygen. The reaction of 2·ClO4 with dioxygen affords 2-amino-3H-phenoxazin-3-one, an auto-oxidation product of 2-aminophenol, whereas complexes 3·BPh4, 4·BPh4, 5·ClO4 and 6·ClO4 react with O2 to exhibit C-C bond cleavage of the bound aminophenolates. Complexes 7·ClO4 and 7(Ox)·BPh4 produce a mixture of 4,6-di-tert-butyl-2H-pyran-2-imine and 4,6-di-tert-butyl-2-picolinic acid. Labeling experiments with (18)O2 show the incorporation of one oxygen atom from dioxygen into the cleavage products. The reactivity (and stability) of the intermediate, which directs the course of aromatic ring cleavage reaction, is found to be dependent on the nature of ring substituent. The presence of two tert-butyl groups on the aminophenolate ring in 7·ClO4 makes the complex slow to cleave the C-C

  6. Metal-Catalyzed Azidation of Tertiary C–H Bonds Suitable for Late-Stage Functionalization

    PubMed Central

    Sharma, Ankit


    Some enzymes are able to selectively oxidize unactivated aliphatic C-H bonds to form alcohols; however biological systems do not possess enzymes that are able to catalyze the analogous amination of a C-H bond.1,2 The absence of such chemistry is limiting because nitrogen-containing groups are found in therapeutic agents and clinically useful natural products. In one prominent example, the conversion of the ketone of erythromycin to the –N(Me)CH2– group in azithromycin leads to a compound that can be dosed once daily with a shorter length of treatment.3,4 For such reasons, synthetic chemists are very interested in identifying catalysts that can directly convert C-H bonds to C-N bonds. Most currently used catalysts for C-H bond amination are ill suited for the functionalization of complex molecules, because they require excess substrate or directing groups, harsh reaction conditions, weak or acidic C-H bonds, or reagents containing specialized groups on the nitrogen atom.5-14 Among C-H bond amination reactions, those forming a carbon-nitrogen bond at a tertiary alkyl group would be particularly valuable, because this linkage is difficult to generate enzymatically from ketone or alcohol precursors.15 In this manuscript, we report a mild, selective, iron-catalyzed azidation of tertiary C-H bonds with substrate as limiting reagent. The reaction tolerates aqueous environments and is suitable for “late-stage” functionalization of complex structures. Moreover, this azidation creates the ability to install a range of nitrogen functional groups, including those from bio-orthogonal Huisgen “click” cycloadditions and the Staudinger ligation.16-19 For these reasons, we anticipate this methodology will create opportunities to easily modify natural products, their precursors, and their derivatives to analogs that contain distinct polarity and charge from nitrogen-containing groups. It could also be used to help identify targets of biologically active molecules by

  7. Activation of Si-Si Bonds for Copper(I)-Catalyzed Conjugate Silylation.


    Iannazzo, Laura; Molander, Gary A


    Several alkyl- and vinylsilanes were prepared through the copper(I)-catalyzed conjugate silylation of α,β-unsaturated compounds. Optimal reaction conditions were first investigated to realize the conjugate addition of a nucleophilic silicon species to poorly electrophilic acceptors such as phenylvinyl sulfone by cleavage of the Si-Si bond of a disilane reagent. The scope of this reaction was extended to various electrophiles bearing different electron-withdrawing groups and afforded the desired substituted alkyl- and vinylsilanes. Among the wide range of commercially available disilanes, the reactivities of alkyl-, aryl-, and ethoxydisilane were also examined. PMID:23204924

  8. Activation of Si–Si Bonds for Copper(I)-Catalyzed Conjugate Silylation

    PubMed Central

    Iannazzo, Laura; Molander, Gary A.


    Several alkyl- and vinylsilanes were prepared through the copper(I)-catalyzed conjugate silylation of α,β-unsaturated compounds. Optimal reaction conditions were first investigated to realize the conjugate addition of a nucleophilic silicon species to poorly electrophilic acceptors such as phenylvinyl sulfone by cleavage of the Si–Si bond of a disilane reagent. The scope of this reaction was extended to various electrophiles bearing different electron-withdrawing groups and afforded the desired substituted alkyl- and vinylsilanes. Among the wide range of commercially available disilanes, the reactivities of alkyl-, aryl-, and ethoxydisilane were also examined. PMID:23204924

  9. Gold-catalyzed homogeneous oxidative C-O bond formation: efficient synthesis of 1-benzoxyvinyl ketones.


    Peng, Yu; Cui, Li; Zhang, Guozhu; Zhang, Liming


    A novel Au-catalyzed homogeneous oxidative C-O bond-forming reaction involving a Au(I)/Au(III) catalytic cycle is developed. Mechanistic studies reveal the involvement of a unique intramolecular carboxy migration. From readily available propargylic benzoates, this chemistry allows efficient access to captodative alkenes and dienones, demonstrating the synthetic potential of incorporating Au(I)/Au(III) catalytic cycles into contemporary Au chemistry. The unique reactivity and the mechanistic insights would help open a new research area in gold catalysis. PMID:19301899

  10. Cobalt-Catalyzed, Aminoquinoline-Directed Coupling of sp2 C–H Bonds with Alkenes

    PubMed Central


    A method for cobalt-catalyzed, aminoquinoline-directed ortho-functionalization of sp2 C–H bonds with alkenes has been developed. Reactions proceed at room temperature in trifluoroethanol solvent, use oxygen from air as an oxidant, and require Mn(OAc)3 as a cocatalyst. Benzoic, heteroaromatic, and acrylic acid aminoquinoline amides react with ethylene as well as mono- and disubstituted alkenes affording products in good yields. Excellent functional group tolerance is observed; halogen, nitro, ether, and unprotected alcohol functionalities are compatible with the reaction conditions. PMID:25146300

  11. C-H activation and C=C double bond formation reactions in iridium ortho-methyl arylphosphane complexes.


    Baratta, Walter; Ballico, Maurizio; Del Zotto, Alessandro; Zangrando, Ennio; Rigo, Pierluigi


    The Vaska-type iridium(I) complex [IrCl(CO){PPh(2)(2-MeC(6)H(4))}(2)] (1), characterized by an X-ray diffraction study, was obtained from iridium(III) chloride hydrate and PPh(2)(2,6-MeRC(6)H(3)) with R=H in DMF, whereas for R=Me, activation of two ortho-methyl groups resulted in the biscyclometalated iridium(III) compound [IrCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)] (2). Conversely, for R=Me the iridium(I) compound [IrCl(CO){PPh(2)(2,6-Me(2)C(6)H(3))}(2)] (3) can be obtained by treatment of [IrCl(COE)(2)](2) (COE=cyclooctene) with carbon monoxide and the phosphane in acetonitrile. Compound 3 in CH(2)Cl(2) undergoes intramolecular C-H oxidative addition, affording the cyclometalated hydride iridium(III) species [IrHCl(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}] (4). Treatment of 2 with Na[BAr(f) (4)] (Ar(f)=3,5-C(6)H(3)(CF(3))(2)) gives the fluxional cationic 16-electron complex [Ir(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}(2)][BAr(f) (4)] (5), which reversibly reacts with dihydrogen to afford the delta-agostic complex [IrH(CO){PPh(2)(2,6-CH(2)MeC(6)H(3))}{PPh(2)(2,6-Me(2)C(6)H(3))}][BAr(f)(4)] (6), through cleavage of an Ir-C bond. This species can also be formed by treatment of 4 with Na[BAr(f)(4)] or of 2 with Na[BAr(f)(4)] through C-H oxidative addition of one ortho-methyl group, via a transient 14-electron iridium(I) complex. Heating of the coordinatively unsaturated biscyclometalated species 5 in toluene gives the trans-dihydride iridium(III) complex [IrH(2)(CO){PPh(2)(2,6-MeC(6)H(3)CH=CHC(6)H(3)Me-2,6)PPh(2)}][BAr(f) (4)] (7), containing a trans-stilbene-type terdentate ligand, as result of a dehydrogenative carbon-carbon double bond coupling reaction, possibly through an iridium carbene species. PMID:17535000

  12. Rhodium-catalyzed silylation of aromatic carbon-hydrogen bonds in 2-arylpyridines with disilane.


    Tobisu, Mamoru; Ano, Yusuke; Chatani, Naoto


    The rhodium(I)-catalyzed regioselective silylation of the ortho carbon-hydrogen bond in 2-arylpyridines with disilane is described. For example, the reaction of 2-(2-methylphenyl)pyridine with 2 equivalents of hexamethyldisilane in the presence of 5 mol % [RhCl(cod)](2) (cod=1,5-cyclooctadiene) in o-xylene at 130 degrees C for 15 h gave 2-[2-methyl-6-(trimethylsilyl)phenyl]pyridine in 86 % yield. In contrast to silylation with hydrosilanes, hydrogen acceptors are not required to achieve high conversion. A variety of substituents, including alkoxy, amine, ester, and fluorinated groups, are compatible with this catalysis. When substrates containing two ortho C-H bonds are used, monosilylated products are obtained selectively by utilizing the 3-methyl-2-pyridyl group as a directing group. PMID:18494014

  13. A structural view on the mechanism of the ribosome-catalyzed peptide bond formation

    PubMed Central

    Simonović, Miljan; Steitz, Thomas A.


    The ribosome is a large ribonucleoprotein particle that translates zgenetic information encoded in mRNA into specific proteins. Its highly conserved active site, the peptidyl-transferase center (PTC), is located on the large (50S) ribosomal subunit and is comprised solely of rRNA, which makes the ribosome the only natural ribozyme with polymerase activity. The last decade witnessed a rapid accumulation of atomic-resolution structural data on both ribosomal subunits as well as on the entire ribosome. This has allowed studies on the mechanism of peptide bond formation at a level of detail that surpasses that for the classical protein enzymes. A current understanding of the mechanism of the ribosome-catalyzed peptide bond formation is the focus of this review. Implications on the mechanism of peptide release are discussed as well. PMID:19595805

  14. Copper-catalyzed oxaziridine-mediated oxidation of C-H bonds.


    Motiwala, Hashim F; Gülgeze, Belgin; Aubé, Jeffrey


    The highly regio- and chemoselective oxidation of activated C-H bonds has been observed via copper-catalyzed reactions of oxaziridines. The oxidation proceeded with a variety of substrates, primarily comprising allylic and benzylic examples, as well as one example of an otherwise unactivated tertiary C-H bond. The mechanism of the reaction is proposed to involve single-electron transfer to the oxaziridines to generate a copper-bound radical anion, followed by hydrogen atom abstraction and collapse to products, with regeneration of the catalyst by a final single-electron transfer event. The involvement of allylic radical intermediates was supported by a radical-trapping experiment with TEMPO. PMID:22830300

  15. Novel dehydrogenase catalyzes oxidative hydrolysis of carbon-nitrogen double bonds for hydrazone degradation.


    Itoh, Hideomi; Suzuta, Tetsuya; Hoshino, Takayuki; Takaya, Naoki


    Hydrazines and their derivatives are versatile artificial and natural compounds that are metabolized by elusive biological systems. Here we identified microorganisms that assimilate hydrazones and isolated the yeast, Candida palmioleophila MK883. When cultured with adipic acid bis(ethylidene hydrazide) as the sole source of carbon, C. palmioleophila MK883 degraded hydrazones and accumulated adipic acid dihydrazide. Cytosolic NAD+- or NADP+-dependent hydrazone dehydrogenase (Hdh) activity was detectable under these conditions. The production of Hdh was inducible by adipic acid bis(ethylidene hydrazide) and the hydrazone, varelic acid ethylidene hydrazide, under the control of carbon catabolite repression. Purified Hdh oxidized and hydrated the C=N double bond of acetaldehyde hydrazones by reducing NAD+ or NADP+ to produce relevant hydrazides and acetate, the latter of which the yeast assimilated. The deduced amino acid sequence revealed that Hdh belongs to the aldehyde dehydrogenase (Aldh) superfamily. Kinetic and mutagenesis studies showed that Hdh formed a ternary complex with the substrates and that conserved Cys is essential for the activity. The mechanism of Hdh is similar to that of Aldh, except that it catalyzed oxidative hydrolysis of hydrazones that requires adding a water molecule to the reaction catalyzed by conventional Aldh. Surprisingly, both Hdh and Aldh from baker's yeast (Ald4p) catalyzed the Hdh reaction as well as aldehyde oxidation. Our findings are unique in that we discovered a biological mechanism for hydrazone utilization and a novel function of proteins in the Aldh family that act on C=N compounds. PMID:18096698

  16. Successive C-C Coupling of Dienes to Vicinally Dioxygenated Hydrocarbons: Ruthenium Catalyzed [4+2] Cycloaddition across the Diol, Hydroxycarbonyl or Dione Oxidation Levels

    PubMed Central

    Geary, Laina M.; Glasspoole, Ben W.; Kim, Mary M.; Krische, Michael J.


    The ruthenium(0) catalyst generated from Ru3(CO)12 and tricyclohexylphosphine or BIPHEP promotes successive C-C coupling of dienes to vicinally dioxygenated hydrocarbons across the diol, hydroxyketone and dione oxidation levels to form products of [4+2] cycloaddition. A mechanism involving diene-carbonyl oxidative coupling followed by intramolecular carbonyl addition from the resulting allylruthenium intermediate is postulated. PMID:23448269

  17. Photoinduced, Copper-Catalyzed Carbon-Carbon Bond Formation with Alkyl Electrophiles: Cyanation of Unactivated Secondary Alkyl Chlorides at Room Temperature.


    Ratani, Tanvi S; Bachman, Shoshana; Fu, Gregory C; Peters, Jonas C


    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. PMID:26491957

  18. Bis(trifluoromethyl)methylene addition to vinyl-terminated SAMs: a gas-phase C-C bond-forming reaction on a surface.


    Adamkiewicz, Malgorzata; O'Hagan, David; Hähner, Georg


    Vinyl-terminated self-assembled monolayers (SAMs) on silicon oxide substrates were chemically modified by the addition of a bis(trifluoromethyl)methylene group in a rare gas-phase C-C bond-forming reaction to directly generate films carrying terminal CF3 groups. The vinyl-terminated films were treated with hexafluoroacetone azine (HFAA) for modification. The films were characterized with ellipsometry, contact angle measurements, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). In this study, we find that for optimized conditions clean reactions occur on a surface between SAMs with terminal olefins and HFAA, and the product is consistent with bis(trifluoromethyl)cyclopropanation formation after nitrogen extrusion. PMID:24806554

  19. Practical carbon-carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation.


    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei


    New carbon-carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp(2))-C(sp(3)) and C(sp(3))-C(sp(3)) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  20. Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation

    PubMed Central

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei


    New carbon–carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  1. Reaction Pathways and Energetics of Etheric C–O Bond Cleavage Catalyzed by Lanthanide Triflates

    SciTech Connect

    Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.


    Efficient and selective cleavage of etheric C-O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C-O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C-O cleavage occurs via a C-H → O-H proton transfer in concert with weakening of the C-O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C-O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

  2. Synthesis of Biaryls through Nickel-Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-Nitrogen Bond Cleavage.


    Shi, Shicheng; Meng, Guangrong; Szostak, Michal


    The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis of widely occurring biaryl compounds through N-C amide bond activation is reported. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents on both coupling partners. The reaction constitutes the first example of the Ni-catalyzed generation of aryl electrophiles from bench-stable amides with potential applications for a broad range of organometallic reactions. PMID:27101428

  3. Enantioselective Aminomethylamination of Conjugated Dienes with Aminals Enabled by Chiral Palladium Complex-Catalyzed C-N Bond Activation.


    Liu, Yang; Xie, Yinjun; Wang, Hongli; Huang, Hanmin


    A novel highly enantioselective aminomethylamination of conjugated dienes with aminals catalyzed by a chiral palladium complex ligated with BINOL-derived chiral diphosphinite has been successfully developed. This reaction proceeds via a Pd-catalyzed cascade C-N bond activation, aminomethylation, and asymmetric allylic amination reaction under mild reaction conditions, providing a unique and efficient strategy for the synthesis of enantiomerically pure allylic 1,3-diamines. PMID:26998813

  4. Silicon-Carbon Bond Formation via Nickel-Catalyzed Cross-Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles.


    Chu, Crystal K; Liang, Yufan; Fu, Gregory C


    A wide array of cross-coupling methods for the formation of C-C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C-heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleophiles to form C-Si bonds. In this study, we address this challenge, establishing that a simple, commercially available nickel catalyst (NiBr2·diglyme) can achieve couplings of alkyl bromides with nucleophilic silicon reagents under unusually mild conditions (e.g., -20 °C); especially noteworthy is our ability to employ unactivated tertiary alkyl halides as electrophilic coupling partners, which is still relatively uncommon in the field of cross-coupling chemistry. Stereochemical, relative reactivity, and radical-trap studies are consistent with a homolytic pathway for C-X bond cleavage. PMID:27187869

  5. Cinchona Urea-Catalyzed Asymmetric Sulfa-Michael Reactions: The Brønsted Acid-Hydrogen Bonding Model.


    Grayson, Matthew N; Houk, K N


    The cinchona alkaloid-derived urea-catalyzed asymmetric conjugate addition of aromatic thiols to cycloalkenones was studied using density functional theory (DFT). Deprotonation of the thiol gives a protonated amine that activates the electrophile by Brønsted acid catalysis, while the urea group binds the nucleophilic thiolate by hydrogen bonding. These results demonstrate the generality of the Brønsted acid-hydrogen bonding transition state (TS) model for cinchona alkaloid catalysis that we recently showed to be favored over Wynberg's widely accepted ion pair-hydrogen bonding model and represent the first detailed mechanistic study of a cinchona urea-catalyzed reaction. The conformation of the catalyst methoxy group has a strong effect on the TS, an effect overlooked in previous mechanistic studies of reactions catalyzed by cinchona alkaloids. PMID:27396591

  6. Rhodium catalyzed chelation-assisted C-H bond functionalization reactions

    PubMed Central

    Colby, Denise A.; Tsai, Andy S.; Bergman, Robert G.; Ellman, Jonathan A.


    Conspectus Over the last several decades, researchers have achieved remarkable progress in the field of organometallic chemistry. The development of metal-catalyzed cross-coupling reactions represents a paradigm shift in chemical synthesis, and today synthetic chemists can readily access carbon-carbon and carbon-heteroatom bonds from a vast array of starting compounds. Although we cannot understate the importance of these methods, the required pre-functionalization to carry out these reactions adds cost and reduces the availability of the starting reagents. The use of C-H bond activation in lieu of pre-functionalization has presented a tantalizing alternative to classical cross-coupling reactions. Researchers have met the challenges of selectivity and reactivity associated with the development of C-H bond functionalization reactions with an explosion of creative advances in substrate and catalyst design. Literature reports on selectivity based on steric effects, acidity, and electronic and directing group effects are now numerous. Our group has developed an array of C-H bond functionalization reactions that take advantage of a chelating directing group, and this Account surveys our progress in this area. The use of chelation control in C-H bond functionalization offers several advantages with respect to substrate scope and application to total synthesis. The predictability and decreased dependence on the inherent stereoelectronics of the substrate generally result in selective and high yielding transformations with broad applicability. The nature of the chelating moiety can be chosen to serve as a functional handle in subsequent elaborations. Our work began with the use of Rh(I) catalysts in intramolecular aromatic C-H annulations, which we further developed to include enantioselective transformations. The application of this chemistry to the simple olefinic C-H bonds found in α,β-unsaturated imines allowed access to highly substituted olefins, pyridines, and

  7. A mechanistic study of Trichoderma reesei Cel7B catalyzed glycosidic bond cleavage.


    Zhang, Yu; Yan, Shihai; Yao, Lishan


    An ONIOM study is performed to illustrate the mechanism of Trichoderma reesei Cel7B catalyzed p-nitrophenyl lactoside hydrolysis. In both the glycosylation and deglycosylation steps, the reaction proceeds in a concerted way, meaning the nucleophilic attack and the glycosidic bond cleavage occur simultaneously. The glycosylation step is rate limiting with a barrier of 18.9 kcal/mol, comparable to the experimental value derived from the kcat measured in this work. The function of four residues R108, Y146, Y170, and D172, which form a hydrogen-bond network involving the substrate, is studied by conservative mutations. The mutants, including R108K, Y146F, Y170F, and D172N, decrease the enzyme activity by about 150-8000-fold. Molecular dynamics simulations show that the mutations disrupt the hydrogen-bond network, cause the substrate to deviate from active binding and hinder either the proton transfer from E201 to O4(+1) or the nucleophilic attack from E196 to C1(-1). PMID:23822607

  8. Recent advances in copper-catalyzed asymmetric coupling reactions.


    Zhou, Fengtao; Cai, Qian


    Copper-catalyzed (or -mediated) asymmetric coupling reactions have received significant attention over the past few years. Especially the coupling reactions of aryl or alkyl halides with nucleophiles became a very powerful tool for the formation of C-C, C-N, C-O and other carbon-heteroatom bonds as well as for the construction of heteroatom-containing ring systems. This review summarizes the recent progress in copper-catalyzed asymmetric coupling reactions for the formation of C-C and carbon-heteroatom bonds. PMID:26734106

  9. Palladium-Catalyzed Allylic C-H Bond Functionalization of Olefins

    NASA Astrophysics Data System (ADS)

    Liu, Guosheng; Wu, Yichen

    Transition metal-mediated carbon-hydrogen bond cleavage and functionalization is a mechanistically interesting and synthetically attractive process. One of the important cases is the removal of a allylic hydrogen from an olefin by a PdII salt to yield a π-allylpalladium complex, followed by nucleophilic attack to efficient produce allylic derivatives. In contrast to the well-known allylic acetoxylation of cyclohexene, the reaction of open-chain olefins is fairly poor until recent several years. Some palladium catalytic systems have been reported to achieve allylic C-H functionalization, including acetoxylation, amination and alkylation of terminal alkenes. In the most of cases, ligand is crucial to the success of the transformation. This review surveys the recent development of palladium-catalyzed allylic C-H functionalziation of alkenes. These results promise a significant increase in the scope of olefin transformation.

  10. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    PubMed Central

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi


    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

  11. Palladium-catalyzed picolinamide-directed iodination of remote ortho-C−H bonds of arenes: Synthesis of tetrahydroquinolines

    PubMed Central

    Nack, William A; Wang, Xinmou; Wang, Bo


    Summary A new palladium-catalyzed picolinamide (PA)-directed ortho-iodination reaction of ε-C(sp2)−H bonds of γ-arylpropylamine substrates is reported. This reaction proceeds selectively with a variety of γ-arylpropylamines bearing strongly electron-donating or withdrawing substituents, complementing our previously reported PA-directed electrophilic aromatic substitution approach to this transformation. As demonstrated herein, a three step sequence of Pd-catalyzed γ-C(sp3)−H arylation, Pd-catalyzed ε-C(sp2)−H iodination, and Cu-catalyzed C−N cyclization enables a streamlined synthesis of tetrahydroquinolines bearing diverse substitution patterns. PMID:27559375

  12. Asymmetric Synthesis of (-)-Incarvillateine Employing an Intramolecular Alkylation via Rh-Catalyzed Olefinic C-H Bond Activation

    SciTech Connect

    Tsai, Andy; Bergman, Robert; Ellman, Jonathan


    An asymmetric total synthesis of (-)-incarvillateine, a natural product having potent analgesic properties, has been achieved in 11 steps and 15.4% overall yield. The key step is a rhodium-catalyzed intramolecular alkylation of an olefinic C-H bond to set two stereocenters. Additionally, this transformation produces an exocyclic, tetrasubstituted alkene through which the bicyclic piperidine moiety can readily be accessed.

  13. Controlling Site Selectivity in Palladium-Catalyzed C–H Bond Functionalization

    PubMed Central

    Neufeldt, Sharon R.; Sanford, Melanie S.


    Conspectus Effective methodology to functionalize C–H bonds requires overcoming the key challenge of differentiating among the multitude of C–H bonds that are present in complex organic molecules. This Account focuses on our work over the past decade toward the development of site-selective Pd-catalyzed C–H functionalization reactions using the following approaches: substrate-based control over selectivity through the use of directing groups (approach 1), substrate control through the use of electronically activated substrates (approach 2), or catalyst-based control (approach 3). In our extensive exploration of the first approach, a number of selectivity trends have emerged for both sp2 and sp3 C–H functionalization reactions that hold true for a variety of transformations involving diverse directing groups. Functionalizations tend to occur at the less-hindered sp2 C–H bond ortho to a directing group, at primary sp3 C–H bonds that are β to a directing group, and, when multiple directing groups are present, at C–H sites proximal to the most basic directing group. Using approach 2, which exploits electronic biases within a substrate, our group has achieved C-2-selective arylation of indoles and pyrroles using diaryliodonium oxidants. The selectivity of these transformations is altered when the C-2 site of the heterocycle is blocked, leading to C–C bond formation at the C-3 position. While approach 3 (catalyst-based control) is still in its early stages of exploration, we have obtained exciting results demonstrating that site selectivity can be tuned by modifying the structure of the supporting ligands on the Pd catalyst. For example, by modulating the structure of N~N bidentate ligands, we have achieved exquisite levels of selectivity for arylation at the α site of naphthalene. Similarly, we have demonstrated that both the rate and site selectivity of arene acetoxylation depend on the ratio of pyridine (ligand) to Pd. Lastly, by switching the ligand

  14. Molecular cloning and characterization of CYP80G2, a cytochrome P450 that catalyzes an intramolecular C-C phenol coupling of (S)-reticuline in magnoflorine biosynthesis, from cultured Coptis japonica cells.


    Ikezawa, Nobuhiro; Iwasa, Kinuko; Sato, Fumihiko


    Cytochrome P450s (P450) play a key role in oxidative reactions in plant secondary metabolism. Some of them, which catalyze unique reactions other than the standard hydroxylation, increase the structural diversity of plant secondary metabolites. In isoquinoline alkaloid biosyntheses, several unique P450 reactions have been reported, such as methylenedioxy bridge formation, intramolecular C-C phenol-coupling and intermolecular C-O phenol-coupling reactions. We report here the isolation and characterization of a C-C phenol-coupling P450 cDNA (CYP80G2) from an expressed sequence tag library of cultured Coptis japonica cells. Structural analysis showed that CYP80G2 had high amino acid sequence similarity to Berberis stolonifera CYP80A1, an intermolecular C-O phenol-coupling P450 involved in berbamunine biosynthesis. Heterologous expression in yeast indicated that CYP80G2 had intramolecular C-C phenol-coupling activity to produce (S)-corytuberine (aporphine-type) from (S)-reticuline (benzylisoquinoline type). Despite this intriguing reaction, recombinant CYP80G2 showed typical P450 properties: its C-C phenol-coupling reaction required NADPH and oxygen and was inhibited by a typical P450 inhibitor. Based on a detailed substrate-specificity analysis, this unique reaction mechanism and substrate recognition were discussed. CYP80G2 may be involved in magnoflorine biosynthesis in C. japonica, based on the fact that recombinant C. japonica S-adenosyl-L-methionine:coclaurine N-methyltransferase could convert (S)-corytuberine to magnoflorine. PMID:18230623

  15. Mild and Selective Catalytic Hydrogenation of the C=C Bond in α,β-Unsaturated Carbonyl Compounds Using Supported Palladium Nanoparticles.


    Nagendiran, Anuja; Pascanu, Vlad; Bermejo Gómez, Antonio; González Miera, Greco; Tai, Cheuk-Wai; Verho, Oscar; Martín-Matute, Belén; Bäckvall, Jan-E


    Chemoselective reduction of the C=C bond in a variety of α,β-unsaturated carbonyl compounds using supported palladium nanoparticles is reported. Three different heterogeneous catalysts were compared using 1 atm of H2 : 1) nano-Pd on a metal-organic framework (MOF: Pd(0) -MIL-101-NH2 (Cr)), 2) nano-Pd on a siliceous mesocellular foam (MCF: Pd(0) -AmP-MCF), and 3) commercially available palladium on carbon (Pd/C). Initial studies showed that the Pd@MOF and Pd@MCF nanocatalysts were superior in activity and selectivity compared to commercial Pd/C. Both Pd(0) -MIL-101-NH2 (Cr) and Pd(0) -AmP-MCF were capable of delivering the desired products in very short reaction times (10-90 min) with low loadings of Pd (0.5-1 mol %). Additionally, the two catalytic systems exhibited high recyclability and very low levels of metal leaching. PMID:27111403

  16. Acetaldehyde partial oxidation on the Au(111) model catalyst surface: C-C bond activation and formation of methyl acetate as an oxidative coupling product

    NASA Astrophysics Data System (ADS)

    Karatok, Mustafa; Vovk, Evgeny I.; Shah, Asad A.; Turksoy, Abdurrahman; Ozensoy, Emrah


    Partial oxidation of acetaldehyde (CH3CHO) on the oxygen pre-covered Au(111) single crystal model catalyst was investigated via Temperature Programmed Desorption (TPD) and Temperature Programmed Reaction Spectroscopy (TPRS) techniques, where ozone (O3) was utilized as the oxygen delivery agent providing atomic oxygen to the reacting surface. We show that for low exposures of O3 and small surface oxygen coverages, two partial oxidation products namely, methyl acetate (CH3COOCH3) and acetic acid (CH3COOH) can be generated without the formation of significant quantities of carbon dioxide. The formation of methyl acetate as the oxidative coupling reaction product implies that oxygen pre-covered Au(111) single crystal model catalyst surface can activate C-C bonds. In addition to the generation of these products; indications of the polymerization of acetaldehyde on the gold surface were also observed as an additional reaction route competing with the partial and total oxidation pathways. The interplay between the partial oxidation, total oxidation and polymerization pathways reveals the complex catalytic chemistry associated with the interaction between the acetaldehyde and atomic oxygen on catalytic gold surfaces.

  17. Intramolecular Interaction, Photoisomerization, and Mechanical C-C Bond Dissociation of 1,2-Di(9-anthryl)benzene and Its Photoisomer: A Fundamental Moiety of Anthracene-Based π-Cluster Molecules.


    Nishiuchi, Tomohiko; Uno, Shin-Ya; Hirao, Yasukazu; Kubo, Takashi


    We report variable and unique properties of 1,2-di(9-anthryl)benzene 1 as a fundamental moiety of anthracene-based π-cluster molecules. Due to a through-space π-conjugation between anthracene units, excimer emission at room temperature and charge delocalized state in radical cation state of 1 could be observed. Photoirradiation to 1 afforded an intramolecular [4 + 4] cyclized anthracene dimer 1' having a high strain energy with long C-C bond that exceeded 1.68 Å, resulting in C-C bond dissociation by simple mechanical grinding. PMID:26828776

  18. Rhodium-catalyzed silylation and intramolecular arylation of nitriles via the silicon-assisted cleavage of carbon-cyano bonds.


    Tobisu, Mamoru; Kita, Yusuke; Ano, Yusuke; Chatani, Naoto


    A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled. PMID:18975946

  19. Cu-Catalyzed Intramolecular Amidation of Unactivated C(sp(3) )-H Bonds To Synthesize N-Substituted Indolines.


    Pan, Fei; Wu, Bin; Shi, Zhang-Jie


    A copper-catalyzed intramolecular amidation of unactivated C(sp(3) )-H bonds to construct indoline derivatives has been developed. Such an amidation proceeded well at primary C-H bonds preferred to secondary C-H bonds. The transformation owned a broad substrate scope. The corresponding indolines were obtained in good to excellent yields. N-Formal and other carbonyl groups were suitable and were easily deprotected and transformed into methyl or long-chained alkyl groups. Preliminary mechanistic studies suggested a radical pathway. PMID:26945702

  20. Copper-Catalyzed Domino Synthesis of 2-Arylthiochromanones through Concomitant C-S Bond Formations Using Xanthate as Sulfur Source.


    Sangeetha, Subramani; Muthupandi, Pandi; Sekar, Govindasamy


    An efficient domino process for the synthesis of thioflavanones has been described using a copper catalyst without addition of any external ligand. A variety of thioflavanones have been synthesized from easily accessible 2'-iodochalcones or 2'-bromochalcones in excellent yield through in situ incorporation of sulfur using xanthate as an odorless sulfur source. This domino process proceeds through Cu-catalyzed C(aryl)-S bond formation by the coupling reaction of xanthate with 2'-halochalcones followed by C-S bond cleavage of thioester then S-C bond formation by intramolecular Michael addition. PMID:26642368

  1. Diversification of ortho-Fused Cycloocta-2,5-dien-1-one Cores and Eight- to Six-Ring Conversion by σ Bond C-C Cleavage.


    Eccleshare, Lee; Lozada-Rodríguez, Leticia; Cooper, Phillippa; Burroughs, Laurence; Ritchie, John; Lewis, William; Woodward, Simon


    Sequential treatment of 2-C6 H4 Br(CHO) with LiC≡CR(1) (R(1) =SiMe3 , tBu), nBuLi, CuBr⋅SMe2 and HC≡CCHClR(2) [R(2) =Ph, 4-CF3 Ph, 3-CNPh, 4-(MeO2 C)Ph] at -50 °C leads to formation of an intermediate carbanion (Z)-1,2-C6 H4 {CA (=O)C≡CB R(1) }{CH=CH(CH(-) )R(2) } (4). Low temperatures (-50 °C) favour attack at CB leading to kinetic formation of 6,8-bicycles containing non-classical C-carbanion enolates (5). Higher temperatures (-10 °C to ambient) and electron-deficient R(2) favour retro σ-bond C-C cleavage regenerating 4, which subsequently closes on CA providing 6,6-bicyclic alkoxides (6). Computational modelling (CBS-QB3) indicated that both pathways are viable and of similar energies. Reaction of 6 with H(+) gave 1,2-dihydronaphthalen-1-ols, or under dehydrating conditions, 2-aryl-1-alkynylnaphthlenes. Enolates 5 react in situ with: H2 O, D2 O, I2 , allylbromide, S2 Me2 , CO2 and lead to the expected C-E derivatives (E=H, D, I, allyl, SMe, CO2 H) in 49-64 % yield directly from intermediate 5. The parents (E=H; R(1) =SiMe3 , tBu; R(2) =Ph) are versatile starting materials for NaBH4 and Grignard C=O additions, desilylation (when R(1) =SiMe) and oxime formation. The latter allows formation of 6,9-bicyclics via Beckmann rearrangement. The 6,8-ring iodides are suitable Suzuki precursors for Pd-catalysed C-C coupling (81-87 %), whereas the carboxylic acids readily form amides under T3P® conditions (71-95 %). PMID:27452351

  2. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    PubMed Central

    Lewis, Jared C.; Bergman, Robert G.; Ellman, Jonathan A.


    Conspectus Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct functionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes our work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. We initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. We then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, we discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. We then synthesized analogous Rh–NHC complexes directly by treating precursors to the intermediate [RhCl(PCy3)2] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazoline, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy3)2 fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, we developed conditions that efficiently and intermolecularly alkylate a variety of heterocycles, including

  3. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    SciTech Connect

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan


    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  4. Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C–H Bond Functionalization Reactions

    PubMed Central

    Sigman, Matthew S.; Werner, Erik W.


    Conspectus The functional group transformations carried out by the palladium-catalyzed Wacker and Heck reactions are radically different, but they are both alkenyl C-H bond functionalization reactions that have found extensive use in organic synthesis. The synthetic community depends heavily on these important reactions, but selectivity issues arising from control by the substrate, rather than control by the catalyst, have prevented the realization of their full potential. Because of important similarities in the respective selectivity-determining nucleopalladation and β-hydride elimination steps of these processes, we posit that the mechanistic insight garnered through the development of one of these catalytic reactions may be applied to the other. In this Account, we detail our efforts to develop catalyst-controlled variants of both the Wacker oxidation and the Heck reaction to address synthetic limitations and provide mechanistic insight into the underlying organometallic processes of these reactions. In contrast to previous reports, we discovered that electrophilic palladium catalysts with non-coordinating counterions allowed for the use of a Lewis basic ligand to efficiently promote TBHP-mediated Wacker oxidation reactions of styrenes. This discovery led to the mechanistically guided development of a Wacker reaction catalyzed by a palladium complex with a bidentate ligand. This ligation may prohibit coordination of allylic heteroatoms, thereby allowing for the application of the Wacker oxidation to substrates that were poorly behaved under classical conditions. Likewise, we unexpectedly discovered that electrophilic Pd-σ-alkyl intermediates are capable of distinguishing between electronically inequivalent C–H bonds during β-hydride elimination. As a result, we have developed E-styrenyl selective oxidative Heck reactions of previously unsuccessful electronically non-biased alkene substrates using arylboronic acid derivatives. The mechanistic insight gained

  5. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation


    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.


    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. Thesemore » results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

  6. Auxiliary-assisted palladium-catalyzed halogenation of unactivated C(sp(3))-H bonds at room temperature.


    Yang, Xinglin; Sun, Yonghui; Sun, Tian-Yu; Rao, Yu


    The direct transformation of unactivated C(sp(3))-H bonds into C-halogen bonds was achieved by palladium catalysis at room temperature with good functional group tolerance. Some drugs and natural products were readily modified by this method. Merged with substitution reaction, newly formed C-X bonds can be transformed into diverse C-O, C-S, C-C and C-N bonds. A preliminary mechanism study demonstrates that solvent is crucial for C-H activation and the C-H activation step is involved in the rate-limiting step. An isolated Pd(ii) intermediate can be transformed into a halogenated product with the retention of conformation which suggests that concerted reductive elimination from Pd(iv) to form a C-X bond was favored. PMID:27095147

  7. Sulfur in coal: Model studies of the role of ArS radicals in C-C and C-S bond formation and structural evolution in coal liquefaction

    SciTech Connect

    Alnajjar, M.S.; Franz, J.A.


    Experiments in this paper show the importance of thiyl radicals in sulfur containing coals during coal liquefaction processes. The presence of arylthiyl radicals enhances the cleavage of C-C, C=C, and C=C bonds in these otherwise refactory systems. Abstraction reactions, 1,2-phenyl migration from sulfur to carbon and displacement reactions at sulfur may be important mechanisms of structural evolution during liquefaction. In addition to cleavage of arylalkyl structures, the results also show that undesirable retrograde formation of inert diaryl- and triarylmethanes may be a consequence of the presence of sulfur and the attending aryl thiol structures. Thus, while a reaction medium including sulfur and hydrogen has been demonstrated to lead to the enhance cleavage of the bibenzyl model structure the present results suggest that retrograde reactions may be significant undesired pathways in coal liquefaction in the presence of sulfur. 17 refs.

  8. A DFT study on the NHC catalysed Michael addition of enols to α,β-unsaturated acyl-azoliums. A base catalysed C-C bond-formation step.


    Domingo, Luis R; Sáez, José A; Arnó, Manuel


    The NHC catalysed nucleophilic additions of enols to α,β-unsaturated acyl-azolium intermediates have been investigated using DFT methods at the MPWB1K/6-31G** computational level. In the direct and the conjugate additions, formation of a hydrogen bond (HB) with the carboxyl oxygen is not sufficient to favour the C-C bond formation as a consequence of the low nucleophilic character of enols. Interestingly, when enols form a HB with the chloride counterion, the activation energies associated with the conjugate addition decrease as a consequence of the increased nucleophilic character of enols and the increased electrophilic character of the 'acyl-azolium + Cl' ion pair. Analysis of the DFT reactivity indices allows establishing a base catalysed C-C bond-formation step promoted by the chloride counterion. PMID:24343422

  9. Iron-catalyzed N-alkylation of azoles via cleavage of an sp3 C-H bond adjacent to a nitrogen atom.


    Xia, Qinqin; Chen, Wanzhi


    Iron-catalyzed direct C-N bond formation between azoles and amides is described. The oxidative coupling reactions of sp(3) C-H bonds adjacent to a nitrogen atom in amides and sulfonamides with the N-H bond in azoles proceeded smoothly in the presence of FeCl(2) and di-tert-butyl peroxide (DTBP). PMID:23025235

  10. Rhodium- and iridium-catalyzed dehydrogenative cyclization through double C-H bond cleavages to produce fluorene derivatives.


    Itoh, Masaki; Hirano, Koji; Satoh, Tetsuya; Shibata, Yu; Tanaka, Ken; Miura, Masahiro


    The rhodium-catalyzed cyclization of a series of 2,2-diarylalkanoic acids in the presence of copper acetate as an oxidant smoothly proceeded through double C-H bond cleavages and subsequent decarboxylation to produce the corresponding fluorene derivatives. The direct cyclization of triarylmethanols also took place efficiently by using an iridium catalyst in place of the rhodium, while the hydroxy function was still intact. PMID:23360206

  11. Rhodium(iii)-catalyzed alkylation of primary C(sp(3))-H bonds with α-diazocarbonyl compounds.


    Hou, Wei; Yang, Yaxi; Wu, Yunxiang; Feng, Huijin; Li, Yuanchao; Zhou, Bing


    Rh(iii)-catalyzed intermolecular chelation-assisted insertion of carbenes derived from α-diazocarbonyl compounds into non-acidic primary sp(3) C-H bonds, for the first time, is reported under mild reaction conditions, thus affording a good complement to previous metal-carbenoid-induced primary C(sp(3))-H insertion reactions. We believe that this method will open up a new avenue for primary sp(3) C-H functionalization with α-diazocarbonyl compounds. PMID:27400766

  12. Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp2 and sp3 carbon-hydrogen bonds.


    Shabashov, Dmitry; Daugulis, Olafs


    We have developed a method for auxiliary-directed, palladium-catalyzed beta-arylation and alkylation of sp(3) and sp(2) C-H bonds in carboxylic acid derivatives. The method employs a carboxylic acid 2-methylthioaniline- or 8-aminoquinoline amide substrate, aryl or alkyl iodide coupling partner, palladium acetate catalyst, and an inorganic base. By employing 2-methylthioaniline auxiliary, selective monoarylation of primary sp(3) C-H bonds can be achieved. If arylation of secondary sp(3) C-H bonds is desired, 8-aminoquinoline auxiliary may be used. For alkylation of sp(3) and sp(2) C-H bonds, 8-aminoquinoline auxiliary affords the best results. Some functional group tolerance is observed and amino- and hydroxy-acid derivatives can be functionalized. Preliminary mechanistic studies have been performed. A palladacycle intermediate has been isolated, characterized by X-ray crystallography, and its reactions have been studied. PMID:20175511

  13. The Rh(ii)-catalyzed formal N-S bond insertion reaction of aryldiazoacetates into N-phenyl-sulfenyl phthalimide.


    Song, Zhuang; Wu, Yizhou; Xin, Tao; Jin, Chao; Wen, Xiaoan; Sun, Hongbin; Xu, Qing-Long


    The Rh(ii)-catalyzed sulfur ylide [1,2]-rearrangement of carbenoids generated from aryldiazoacetates has been realized via N-S bond insertion, generating tertiary sulfides in moderate to excellent yields. This demonstrates the first use of the sulfur ylide [1,2]-rearrangement undergoing N-S bond insertion. This protocol could proceed smoothly with high regioselectivity, low catalyst loading (0.1 mol% Rh2(OAc)4), gram-scale reaction and broad substrate scope. And the product could be converted into glycine derivatives through simple procedures. PMID:27087623

  14. Direct C-C Coupling of CO2 and the Methyl Group from CH4 Activation through Facile Insertion of CO2 into Zn-CH3 σ-Bond.


    Zhao, Yuntao; Cui, Chaonan; Han, Jinyu; Wang, Hua; Zhu, Xinli; Ge, Qingfeng


    Conversion of CO2 and CH4 to value-added products will contribute to alleviating the green-house gas effect but is a challenge both scientifically and practically. Stabilization of the methyl group through CH4 activation and facile CO2 insertion ensure the realization of C-C coupling. In the present study, we demonstrate the ready C-C coupling reaction on a Zn-doped ceria catalyst. The detailed mechanism of this direct C-C coupling reaction was examined based on the results from density functional theory calculations. The results show that the Zn dopant stabilizes the methyl group by forming a Zn-C bond, thus hindering subsequent dehydrogenation of CH4. CO2 can be inserted into the Zn-C bond in an activated bent configuration, with the transition state in the form of a three-centered Zn-C-C moiety and an activation barrier of 0.51 eV. The C-C coupling reaction resulted in the acetate species, which could desorb as acetic acid by combining with a surface proton. The formation of acetic acid from CO2 and CH4 is a reaction with 100% atom economy, and the implementation of the reaction on a heterogeneous catalyst is of great importance to the utilization of the greenhouse gases. We tested other possible dopants including Al, Ga, Cd, In, and Ni and found a positive correlation between the activation barrier of C-C coupling and the electronegativity of the dopant, although C-H bond activation is likely the dominant reaction on the Ni-doped ceria catalyst. PMID:27452233

  15. Cobalt(III)-Catalyzed Synthesis of Indazoles and Furans by C–H Bond Functionalization/Addition/Cyclization Cascades

    PubMed Central


    The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C–H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C–H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C–H bonds. PMID:25494296

  16. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

    SciTech Connect

    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.


    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. These results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce

  17. C-H Bond Oxidation Catalyzed by an Imine-Based Iron Complex: A Mechanistic Insight.


    Olivo, Giorgio; Nardi, Martina; Vìdal, Diego; Barbieri, Alessia; Lapi, Andrea; Gómez, Laura; Lanzalunga, Osvaldo; Costas, Miquel; Di Stefano, Stefano


    A family of imine-based nonheme iron(II) complexes (LX)2Fe(OTf)2 has been prepared, characterized, and employed as C-H oxidation catalysts. Ligands LX (X = 1, 2, 3, and 4) stand for tridentate imine ligands resulting from spontaneous condensation of 2-pycolyl-amine and 4-substituted-2-picolyl aldehydes. Fast and quantitative formation of the complex occurs just upon mixing aldehyde, amine, and Fe(OTf)2 in a 2:2:1 ratio in acetonitrile solution. The solid-state structures of (L1)2Fe(OTf)(ClO4) and (L3)2Fe(OTf)2 are reported, showing a low-spin octahedral iron center, with the ligands arranged in a meridional fashion. (1)H NMR analyses indicate that the solid-state structure and spin state is retained in solution. These analyses also show the presence of an amine-imine tautomeric equilibrium. (LX)2Fe(OTf)2 efficiently catalyze the oxidation of alkyl C-H bonds employing H2O2 as a terminal oxidant. Manipulation of the electronic properties of the imine ligand has only a minor impact on efficiency and selectivity of the oxidative process. A mechanistic study is presented, providing evidence that C-H oxidations are metal-based. Reactions occur with stereoretention at the hydroxylated carbon and selectively at tertiary over secondary C-H bonds. Isotopic labeling analyses show that H2O2 is the dominant origin of the oxygen atoms inserted in the oxygenated product. Experimental evidence is provided that reactions involve initial oxidation of the complexes to the ferric state, and it is proposed that a ligand arm dissociates to enable hydrogen peroxide binding and activation. Selectivity patterns and isotopic labeling studies strongly suggest that activation of hydrogen peroxide occurs by heterolytic O-O cleavage, without the assistance of a cis-binding water or alkyl carboxylic acid. The sum of these observations provides sound evidence that controlled activation of H2O2 at (LX)2Fe(OTf)2 differs from that occurring in biomimetic iron catalysts described to date. PMID

  18. Nickel-Catalyzed Reductive Couplings.


    Wang, Xuan; Dai, Yijing; Gong, Hegui


    The Ni-catalyzed reductive coupling of alkyl/aryl with other electrophiles has evolved to be an important protocol for the construction of C-C bonds. This chapter first emphasizes the recent progress on the Ni-catalyzed alkylation, arylation/vinylation, and acylation of alkyl electrophiles. A brief overview of CO2 fixation is also addressed. The chemoselectivity between the electrophiles and the reactivity of the alkyl substrates will be detailed on the basis of different Ni-catalyzed conditions and mechanistic perspective. The asymmetric formation of C(sp(3))-C(sp(2)) bonds arising from activated alkyl halides is next depicted followed by allylic carbonylation. Finally, the coupling of aryl halides with other C(sp(2))-electrophiles is detailed at the end of this chapter. PMID:27573395

  19. Phosphorus-carbon bond formation by lewis Acid catalyzed/mediated addition of silylphosphines.


    Hayashi, Minoru; Matsuura, Yutaka; Nishimura, Yasunobu; Yamasaki, Toshikazu; Imai, Yoshito; Watanabe, Yutaka


    Triethylaluminum-catalyzed/mediated addition of a silylphosphine to aldehydes and epoxides is described. Organophosphines containing a silyloxy group at the alpha- or beta-position on the alkyl substituent are successfully prepared in good yields. PMID:17784776

  20. Copper-catalyzed intramolecular direct amination of sp2 C-H bonds for the synthesis of N-aryl acridones.


    Zhou, Wang; Liu, Yong; Yang, Youqing; Deng, Guo-Jun


    A copper-catalyzed approach for the synthesis of N-aryl acridones via sp(2) C-H bond amination using air as oxidant under neutral conditions is disclosed. This reaction not only provides a complementary method for synthesizing medicinally important acridones, but also offers a new strategy for sp(2) C-H bond amination. PMID:23010788

  1. Formation of C(sp(3) )-C(sp(3) ) Bonds through Nickel-Catalyzed Decarboxylative Olefin Hydroalkylation Reactions.


    Lu, Xi; Xiao, Bin; Liu, Lei; Fu, Yao


    Olefins and carboxylic acids are among the most important feedstock compounds. They are commonly found in natural products and drug molecules. We report a new reaction of nickel-catalyzed decarboxylative olefin hydroalkylation, which provides a novel practical strategy for the construction of C(sp(3) )-C(sp(3) ) bonds. This reaction can tolerate a variety of synthetically relevant functional groups and shows good chemo- and regioselectivity. It enables cross-coupling of complex organic molecules containing olefin groups and carboxylic acid groups in a convergent fashion. PMID:27245257

  2. Rh-Catalyzed Direct Amination of Unactivated C(sp(3) )-H bond with Anthranils Under Mild Conditions.


    Tang, Conghui; Zou, Miancheng; Liu, Jianzhong; Wen, Xiaojin; Sun, Xiang; Zhang, Yiqun; Jiao, Ning


    C-N Bond formation is of great significance due to the ubiquity of nitrogen-containing compounds. Here, a mild and efficient Rh(III) -catalyzed C(sp(3) )-H aryl amination reaction is reported. Anthranil is employed as the nitrogen source with 100 % atom efficiency. This C-H amination reaction exhibits broad substrate scope without using any external oxidants. Mechanistic studies including rhodacycle intermediates, H-D exchange, kinetic isotope effect (KIE) experiments, and in situ IR are presented. PMID:27258824

  3. A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp(2) C-H Bond Amination.


    Roane, James; Daugulis, Olafs


    An operationally simple and general method for copper-catalyzed, aminoquinoline-assisted amination of β-C(sp(2))-H bonds of benzoic acid derivatives is reported. The reaction employs Cu(OAc)2 or (CuOH)2CO3 catalysts, an amine coupling partner, and oxygen from air as a terminal oxidant. Exceptionally high generality with respect to amine coupling partners is observed. Specifically, primary and secondary aliphatic and aromatic amines, heterocycles, such as indoles, pyrazole, and carbazole, sulfonamides, as well as electron-deficient aromatic and heteroaromatic amines are competent coupling components. PMID:26990413

  4. Protease-catalyzed peptide synthesis using inverse substrates: the synthesis of Pro-Xaa-bonds by trypsin.


    Schellenberger, V; Schellenberger, U; Jakubke, H D; Zapevalova, N P; Mitin, Y V


    Benzyloxycarbonyl-L-proline p-guanidinophenyl ester is an "inverse substrate" for trypsin; i.e., the cationic center is included in the leaving group instead of being in the acyl moiety. This substrate can be used in trypsin-catalyzed acyl-transfer reactions leading to the synthesis of Pro-Xaa peptide bonds. The reaction proceeds about 20 times slower than reaction with similar alanine-containing substrates, but the ratio between synthesis and hydrolysis is more favorable. The investigation of a series of nucleophiles led to information about the specificity of the process. Nucleophiles differing only in the P(1)'-position show an increasing acyl transfer efficiency in the order Phe < Gly < Ley < Ser < Ala < lle. C terminal elongation of the nucleophiles is of minor influence on their efficiency. The formation of an H bond between the acyl-enzyme and the nucleophile seems to play an important role in the aminolysis of the acyl-enzyme. PMID:18600766

  5. Pd-catalyzed β-selective direct C-H bond arylation of thiophenes with aryltrimethylsilanes.


    Funaki, Kenji; Sato, Tetsuo; Oi, Shuichi


    Direct arylation of thiophenes and benzothiophenes with aryltrimethylsilanes was effectively catalyzed by PdCl(2)(MeCN)(2) in the presence of CuCl(2) as an oxidant. The reaction preferentially occurred at the β-position of both thiophenes and benzothiophenes. PMID:23214502

  6. FeF(3) catalyzed cascade C-C and C-N bond formation: synthesis of differentially substituted triheterocyclic benzothiazole functionalities under solvent-free condition.


    Atar, Amol B; Jeong, Yeon Tae


    A series of diverse polyfunctionalized triheterocyclic benzothiazoles were easily prepared in excellent yields via the Biginelli reaction of 2-aminobenzothiazole with substituted benzaldehydes and α-methylene ketones using FeF(3) as an expeditious catalyst under solvent-free conditions. The protocol provides a practical and straightforward approach toward highly functionalized triheterocyclic benzothiazole derivatives in excellent yields. The reaction was conveniently promoted by FeF(3) and the catalyst could be recovered easily after the reaction and reused without any loss of its catalytic activity. The advantageous features of this methodology are high atom economy, operational simplicity, shorter reaction time, convergence, and facile automation. PMID:24504377

  7. Oxo-rhenium catalyzed reductive coupling and deoxygenation of alcohols.


    Kasner, Gabrielle R; Boucher-Jacobs, Camille; Michael McClain, J; Nicholas, Kenneth M


    Representative benzylic, allylic and α-keto alcohols are deoxygenated to alkanes and/or reductively coupled to alkane dimers by reaction with PPh3 catalyzed by (PPh3)2ReIO2 (1). The newly discovered catalytic reductive coupling reaction is a rare C-C bond-forming transformation of alcohols. PMID:27174412

  8. Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds


    Hartwig, John F.; Kawatsura, Motoi; Loeber, Oliver


    The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

  9. Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO.


    Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng


    With atmospheric oxygen as the oxidant, a novel copper(I)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation. PMID:22728918

  10. Copper-catalyzed oxidative N-S bond formation for the synthesis of N-sulfenylimines.


    Lee, Chan; Wang, Xi; Jang, Hye-Young


    Despite the remarkable success of the copper-catalyzed oxidative coupling reaction, direct cross-coupling of amines and thiols for the synthesis of N-sulfenylimines has not been previously reported. Using commercially available copper catalysts (CuI) and oxygen as an environmentally benign oxidant, synthetically useful N-sulfenylimines were prepared from amines and thiols in good yields without overoxidation of sulfur atoms. PMID:25685885

  11. An approach to benzophosphole oxides through silver- or manganese-mediated dehydrogenative annulation involving C-C and C-P bond formation.


    Unoh, Yuto; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro


    Benzophosphole construction was achieved through the Ag(I) -mediated dehydrogenative annulation of phenylphosphine oxides with internal alkynes in a process involving CC and CP bond formation. A wide range of asymmetrical phenylacetylenes could be employed and the reactions proceeded with perfect regioselectivity. Moreover, the annulation could be conducted even at room temperature when a Mn(III) promoter was used in place of Ag(I) . PMID:24127410

  12. Radical S-adenosylmethionine enzyme catalyzed thioether bond formation in sactipeptide biosynthesis.


    Flühe, Leif; Marahiel, Mohamed A


    Sactipeptides represent a new emerging class of ribosomally assembled and posttranslationally modified peptides that show diverse bioactivities. Their common hallmark is an intramolecular thioether bond that crosslink the sulfur atom of a cysteine residue with the α-carbon of an acceptor amino acid. This review summarizes recent achievements concerning the biosynthesis of sactipeptides in general and with special focus on the common enzymatic radical SAM mechanism leading to the thioether linkage formation. In addition this mechanism is compared to the mechanism of thioether bond formation during lanthipeptide biosynthesis and to other radical based thioether bond forming reactions. PMID:23891473

  13. Rhenium-Catalyzed Synthesis of 1,3-Diiminoisoindolines via Insertion of Carbodiimides into a C-H Bond of Aromatic and Heteroaromatic Imidates.


    Wang, Zijia; Sueki, Shunsuke; Kanai, Motomu; Kuninobu, Yoichiro


    The rhenium-catalyzed synthesis of 1,3-diiminoisoindolines and their related compounds from aromatic or heteroaromatic imidates and carbodiimides are reported via C-H bond activation. This reaction is the first example of a transition-metal-catalyzed insertion of carbodiimides into an aromatic or heteroaromatic C-H bond and a novel method for synthesizing 1,3-diiminoisoindolines and their related compounds. Unsymmetrical 1,3-diiminoisoindolines were easily obtained using this method. The reaction proceeded in good to excellent yield using a variety of substrates. PMID:27153181

  14. The Catalytic Conversion of C1-Cn Hydrocarbons to Olefins and Hydrogen: Microwave-Assisted C-C and C-H Bond Activation

    SciTech Connect

    Tanner, Dennis D.; Kandanarachchi, Pramod; Ding, Qizhu; Shao, Huawu; Vizitiu, Despina; Franz, James A.


    The gas phase carbon catalyzed microwave promoted conversion of methane to ethylene, ethane and acetylene and hydrogen is reported. A selection of C1-C4 hydrocarbons, hexadecane, and a cyclic hydrocarbon, cyclodecane, were also subjected to microwave conversion, resulting primarily in a-olefins, ethylene and hydrogen. For methane conversion, the products are reminiscent of those found in methane pyrolysis. Microwave induced cleavage of the liquid hydrocarbons provides conditions for the stabilization, by rapid thermal quenching in ambient temperature liquid reagent, of products such as terminal olefins that would be labile under conventional (thermal bath) pyrolysis reaction conditions. The reactions of long chain acyclic and cyclic hydrocarbons involve high temperatures in the region of the spark leading to a cascade of unimolecular scission reactions from initially formed biradicals from cycloalkanes or radical pairs from linear alkanes, largely to the exclusion of intermolecular radical-radical and radical-molecule reactions. The observed products are discussed in terms of the thermochemistry and dynamics of high temperature unimolecular biradical and radical decomposition reactions, and mechanisms involving reactive surface metal sites. The reaction rates of alkanes were found to increase with the molecular weight of the reactants. Mechanistic pathways consistent with these results are discussed.

  15. General and facile method for exo-methlyene synthesis via regioselective C-C double-bond formation using a copper-amine catalyst system.


    Nishikata, Takashi; Nakamura, Kimiaki; Itonaga, Kohei; Ishikawa, Shingo


    In this study, for distal-selective β-hydride elimination to produce exomethylene compounds with a newly formed Csp(3)-Csp(3) bond between tertiary alkyl halides and α-alkylated styrenes, a combination of a Cu(I) salt and a pyridine-based amine ligand (TPMA) is found to be a very efficient catalyst system. The yields and regioselectivities were high, and the regioselectivity was found to be dependent on the structure of the alkyl halide, with bulky alkyl halides showing the highest distal selectivities. PMID:25315319

  16. Does C-C bonding proceed during exposure of adequate metal surfaces to CH{sub 4}? Reply to {open_quotes}Comment by Z. Hlavathy, Z. Paal, and P. Tetenyi{close_quotes}

    SciTech Connect

    Amaraiglio, A.; Pareja, P.; Amariglio, H.


    The comments, results, and reflections presented by Hlavathy and co-workers in their Letter aim at demonstrating that C-C bonding between CH{sub x} adspecies, formed upon exposure of Pt to CH{sub 4}, can proceed as well during the exposure itself as during further exposure to H{sub 2}. This possibility was implicitly put forward because they thought that a tight parallelism exists between the interactions of CH{sub 4} and CO with a metal surface, provided that the exposure to CH{sub 4} is carried out at a high enough temperature (450{degrees}C). In both cases these authors assumed that three kinds of carbon, C{sub {alpha}}, C{sub {beta}}, and C{sub {gamma}}, can be formed, C{sub {alpha}} being the main species responsible for the production of CH{sub 4} and of the C{sub 2}, alkanes obtained when the metal was further contacted with H{sub 2} at 100{degrees}C. As they argued that C{sub {alpha}} (also named carbidic carbon) has only metal atoms in its first coordination shell, they were implicitly led it that C-C bonding must take place during the hydrogenation step. The authors have not denied this possibility, but they have suggested that different situations can result from exposures to CH{sub 4} conducted at temperatures much lower than those used by Koerts et al.. 13 refs.

  17. An efficient and general route to reduced polypropionates via Zr-catalyzed asymmetric CC bond formation.


    Negishi, Ei-Ichi; Tan, Ze; Liang, Bo; Novak, Tibor


    An efficient and general method for the synthesis of reduced polypropionates has been developed through the application of asymmetric carboalumination of alkenes catalyzed by dichlorobis(1-neomenthylindenyl)zirconium [(NMI)(2)ZrCl(2)]. In this investigation, attention has been focused on those reduced polypropionates that are alpha-monoheterofunctional and either omega-ethyl or omega-n-propyl. The reaction of 3-buten-1-ol with triethylaluminum (Et(3)Al) or tripropylaluminum ((n)Pr(3)Al) in the presence of (NMI)(2)ZrCl(2) and isobutylaluminoxane gave, after protonolysis, (R)-3-methyl-1-pentanol as well as (R)- and (S)-3-methyl-1-hexanols in 88-92% yield in 90-92% enantiomeric excess in one step. These 3-monomethyl-1-alkanols were then converted to two stereoisomers each of 2,4-dimethyl-1-hexanols and 2,4-dimethyl-1-heptanols via methylalumination catalyzed by (NMI)(2)ZrCl(2) and methylaluminoxane followed by oxidation with O(2). The four-step (or three-isolation-step) protocol provided syn-2,4-dimethyl-1-alkanols of >/=98% stereoisomeric purity in approximately 50% overall yields, whereas (2S,4R)-2,4-dimethyl-1-hexanol of comparable purity was obtained in 40% overall yield. Commercial availability of (S)-2-methyl-1-butanol as a relatively inexpensive material suggested its use in the synthesis of (2S,4S)- and (2R,4S)-2,4-dimethyl-1-hexanols via a three-step protocol consisting of (i) iodination, (ii) zincation followed by Pd-catalyzed vinylation, and (iii) Zr-catalyzed methylalumination followed by oxidation with O(2). This three-step protocol is iterative and applicable to the synthesis of reduced polypropionates containing three or more branching methyl groups, rendering this method for the synthesis of reduced polypropionates generally applicable. Its synthetic utility has been demonstrated by preparing the side chain of zaragozic acid A and the C11-C20 fragment of antibiotics TMC-151 A-F. PMID:15073327

  18. A meta-selective copper-catalyzed C-H bond arylation.


    Phipps, Robert J; Gaunt, Matthew J


    For over a century, chemical transformations of benzene derivatives have been guided by the high selectivity for electrophilic attack at the ortho/para positions in electron-rich substrates and at the meta position in electron-deficient molecules. We have developed a copper-catalyzed arylation reaction that, in contrast, selectively substitutes phenyl electrophiles at the aromatic carbon-hydrogen sites meta to an amido substituent. This previously elusive class of transformation is applicable to a broad range of aromatic compounds. PMID:19299616

  19. Palladium-Catalyzed Carbonylative Cyclization of Arenes by C-H Bond Activation with DMF as the Carbonyl Source.


    Chen, Jianbin; Feng, Jian-Bo; Natte, Kishore; Wu, Xiao-Feng


    A novel palladium-catalyzed CO-gas- and autoclave-free protocol for the synthesis of 11H-pyrido[2,1-b]quinazolin-11-ones has been developed. Quinazolinones, which are omnipresent motif in many pharmaceuticals and agrochemicals, were prepared in good yields by C-H bond activation and annulation using DMF as the CO surrogate. A (13) CO-labelled DMF control experiment demonstrated that CO gas was released from the carbonyl of DMF with acid as the promotor. The kinetic isotope effect (KIE) value indicated that the C-H activation step may not be involved in the rate-determining step. This methodology is operationally simple and showed a broad substrate scope with good to excellent yields. PMID:26406903

  20. Silver-catalyzed silicon-hydrogen bond functionalization by carbene insertion.


    Iglesias, M José; Nicasio, M Carmen; Caballero, Ana; Pérez, Pedro J


    The catalytic functionalization of silicon-hydrogen bonds by means of the insertion of carbene units :CHCO(2)Et from ethyl diazoacetate (EDA) has been achieved using a silver-based catalyst, constituting the first example of this metal to promote this transformation. Competition experiments have revealed that the relative reactivity of substituted silanes depends on the bond dissociation energy of the Si-H bond (tertiary > secondary > primary for ethyl substituted). In the presence of bulky substituents such order reverts to secondary > primary ≈ tertiary (for phenyl substituted). Screening with other diazo compounds has shown that N(2)C(Ph)CO(2)Et displays similar reactivity to that of EDA, whereas other N(2)C(R)CO(2)Et (R = Me, CO(2)Et) gave lower conversions. PMID:23114570

  1. Nickel-Catalyzed Decarbonylative Borylation of Amides: Evidence for Acyl C-N Bond Activation.


    Hu, Jiefeng; Zhao, Yue; Liu, Jingjing; Zhang, Yemin; Shi, Zhuangzhi


    A nickel/N-heterocyclic carbene catalytic system has been established for decarbonylative borylation of amides with B2 nep2 by C-N bond activation. This transformation shows good functional-group compatibility and can serve as a powerful synthetic tool for late-stage borylation of amide groups in complex compounds. More importantly, as a key intermediate, the structure of an acyl nickel complex was first confirmed by X-ray analysis. Furthermore, the decarbonylative process was also observed. These findings confirm the key mechanistic features of the acyl C-N bond activation process. PMID:27258597

  2. Methanol conversion to hydrocarbons over zeolite H-ZSM-5: Investigation of the role of CO and ketene in the formation of the initial C-C bond

    SciTech Connect

    Hutchings, G.J.; Johnston, P. ); Hunter, R. ); Van Rensburg, L.J. )


    Mechanistic studies concerning the formation of the initial carbon-carbon bond in the methanol conversion reaction over zeolite H-ZSM-5 are described and discussed. In particular, the possible roles of CO as a reaction intermediate or as a catalyst, via the formation of ketene, are evaluated. Experiments using [sup 13]CH[sub 3]OH/[sup 12]CO reactant mixtures demonstrate that no CO is incorporated into ethene, the primary product of this reaction. In addition, CO is found to have no significant effect on the induction period for this reaction. Model experiments for the methylation of ketene by reaction with Me[sub 2]SO[sub 4] and Me[sub 3]O[sup +]SbCl[sub 6][sup [minus

  3. Chlorination-Promoted Skeletal-Cage Transformations of C88 Fullerene by C2 Losses and a C-C Bond Rotation.


    Yang, Shangfeng; Wei, Tao; Scheurell, Kerstin; Kemnitz, Erhard; Troyanov, Sergey I


    High-temperature chlorination of fullerene C88 (isomer 33) with VCl4 gives rise to skeletal transformations affording several nonclassical (NC) fullerene chlorides, C86 (NC1)Cl24/26 and C84 (NC2)Cl26 , with one and two heptagons, respectively, in the carbon cages. The branched skeletal transformation including C2 losses as well as a Stone-Wales rearrangement has been comprehensively characterized by the structure determination of two intermediates and three final chlorination products. Quantum-chemical calculations demonstrate that the average energy of the C-Cl bond is significantly increased in chlorides of nonclassical fullerenes with a large number of chlorinated sites of pentagon-pentagon adjacency. PMID:26332709

  4. Reusable ionic liquid-catalyzed oxidative coupling of azoles and benzylic compounds via sp(3) C-N bond formation under metal-free conditions.


    Liu, Wenbo; Liu, Chenjiang; Zhang, Yonghong; Sun, Yadong; Abdukadera, Ablimit; Wang, Bin; Li, He; Ma, Xuecheng; Zhang, Zengpeng


    The heterocyclic ionic liquid-catalyzed direct oxidative amination of benzylic sp(3) C-H bonds via intermolecular sp(3) C-N bond formation for the synthesis of N-alkylated azoles under metal-free conditions is reported for the first time. The catalyst 1-butylpyridinium iodide can be recycled and reused with similar efficacies for at least eight cycles. PMID:26060993

  5. Interaction of a pseudo-π C-C bond with cuprous and argentous chlorides: Cyclopropane⋯CuCl and cyclopropane⋯AgCl investigated by rotational spectroscopy and ab initio calculations.


    Zaleski, Daniel P; Mullaney, John C; Bittner, Dror M; Tew, David P; Walker, Nicholas R; Legon, Anthony C


    Strongly bound complexes (CH2)3⋯MCl (M = Cu or Ag), formed by non-covalent interaction of cyclopropane and either cuprous chloride or argentous chloride, have been generated in the gas phase by means of the laser ablation of either copper or silver metal in the presence of supersonically expanded pulses of a gas mixture containing small amounts of cyclopropane and carbon tetrachloride in a large excess of argon. The rotational spectra of the complexes so formed were detected with a chirped-pulse, Fourier transform microwave spectrometer and analysed to give rotational constants and Cu and Cl nuclear quadrupole coupling constants for eight isotopologues of each of (CH2)3⋯CuCl and (CH2)3⋯AgCl. The geometry of each of these complexes was established unambiguously to have C(2v) symmetry, with the three C atoms coplanar, and with the MCl molecule lying along a median of the cyclopropane C3 triangle. This median coincides with the principal inertia axis a in each of the two complexes (CH2)3⋯MCl. The M atom interacts with the pseudo-π bond linking the pair of equivalent carbon atoms (F)C (F = front) nearest to it, so that M forms a non-covalent bond to one C-C edge of the cyclopropane molecule. The (CH2)3⋯MCl complexes have similar angular geometries to those of the hydrogen- and halogen-bonded analogues (CH2)3⋯HCl and (CH2)3⋯ClF, respectively. Quantitative details of the geometries were determined by interpretation of the observed rotational constants and gave results in good agreement with those from ab initio calculations carried out at the CCSD(T)(F12*)/aug-cc-pVTZ-F12 level of theory. Interesting geometrical features are the lengthening of the (F)C-(F)C bond and the shrinkage of the two equivalent (B)C-(F)C (B = back) bonds relative to the C-C bond in cyclopropane itself. The expansions of the (F)C-(F)C bond are 0.1024(9) Å and 0.0727(17) Å in (CH2)3⋯CuCl and (CH2)3⋯AgCl, respectively, according to the determined r0 geometries. The C-C bond

  6. Metalation dictates remote regioselectivity: ruthenium-catalyzed functionalization of meta C(Ar)-H Bonds.


    Juliá-Hernández, Francisco; Simonetti, Marco; Larrosa, Igor


    Remote control: The title reaction is effective for the sulfonation and alkylation of arenes bearing directing groups. Initial ortho metalation of the substrate forms an intermediate which does not evolve towards functionalization at the CM bond. Instead, the ruthenium catalyst acts as a strong electron-donating group, thus directing a remote electrophilic attack. PMID:24030678

  7. Trends in Aromatic Oxidation Reactions Catalyzed by Cytochrome P450 Enzymes: A Valence Bond Modeling.


    Shaik, Sason; Milko, Petr; Schyman, Patric; Usharani, Dandamudi; Chen, Hui


    The mixed density functional theory (DFT) and valence bond study described herein focuses on the activation of 17 benzene derivatives by the active species of Cytochrome P450, so-called Compound I (Cpd I), as well as by the methoxy radical, as a potentially simple model of Cpd I (Jones, J. P.; Mysinger, M.; Korzekwa, K. R. Drug Metab. Dispos. 2002, 30, 7-12). Valence bond modeling is employed to rationalize the P450 mechanism and its spin-state selectivity from first principles of electronic structure and to predict activation energies independently, using easily accessible properties of the reactants: the singlet-triplet excitation energies, the ionization potentials of the aromatics, and the electron affinity of Cpd I and/or of the methoxy radical. It is shown that the valence bond model rationalizes all the mechanistic aspects and predicts activation barriers (for 35 reactions) with reasonable accuracy compared to the DFT barriers with an average deviation of ±1.0 kcal·mol(-1) (for DFT barriers, see: Bathelt, C. M.; Ridder, L.; Mulholland, A. J.; Harvey, J. N. Org. Biomol. Chem. 2004, 2, 2998-3005). The valence bond modeling also reveals the mechanistic similarities between the P450 Cpd I and methoxy reactions and enables one to make predictions of barriers for reactions from other studies. PMID:26596155

  8. Copper-catalyzed phosphorylation of sp(2) C-H bonds.


    Wang, Shan; Guo, Rui; Wang, Gao; Chen, Shan-Yong; Yu, Xiao-Qi


    The phosphorylation of the ortho C-H bonds in benzamides containing an 8-aminoquinoline moiety as a bidentate directing group with H-phosphonates using copper as a catalyst under mild temperature conditions is described. This method shows high functional group compatibility and selectively gives mono-substituted products. PMID:25204577

  9. A gold-catalyzed unique cycloisomerization of 1,5-enynes: efficient formation of 1-carboxycyclohexa-1,4-dienes and carboxyarenes.


    Wang, Shaozhong; Zhang, Liming


    A novel Au-catalyzed migratory cycloisomerization strategy is advanced. Implementation of this strategy led to the development of a unique Au-catalyzed 1,5-enyne cycloisomerizatioin involving carboxy migration and Au-mediated C-C single bond formation. 1-Carboxycyclohexa-1,4-dienes and carboxyarenes can be prepared with good efficiency and with flexible substitution patterns. PMID:17076498

  10. Application of Thio-Ugi Adducts for the Preparation of Benzo[b]thiophene and S-Heterocycle Library via Copper Catalyzed Intramolecular C-S Bond Formation.


    Kim, Yong-Sang; Kwak, Se Hun; Gong, Young-Dae


    Fused heterocycles, such as benzo[b]thiophene, thiochroman, benzo[b][1,4]thiazine, and 1,4-benzothiazepine were generated from thio-Ugi adducts containing a thioamide group through copper-catalyzed intramolecular C-S bond formation under microwave irradiation. PMID:25961783

  11. Formation of C(sp(3))-C(sp(3)) Bonds by Palladium Catalyzed Cross-Coupling of α-Diazoketones and Allylboronic Acids.


    Belhomme, Marie-Charlotte; Wang, Dong; Szabó, Kálmán J


    Palladium catalyzed cross-coupling of allylboronic acids with α-diazoketones was studied. The reaction selectively affords the linear allylic product. The reaction proceeds with formation of a new C(sp(3))-C(sp(3)) bond. The reaction was performed without an external oxidant, likely without the Pd-catalyst undergoing redox reactions. PMID:27166509

  12. 3-Component synthesis of α-substituted sulfonamides via Brønsted acid-catalyzed C(sp(3))-H bond functionalization of 2-alkylazaarenes.


    Beisel, T; Kirchner, J; Kaehler, T; Knauer, J; Soltani, Y; Manolikakes, G


    A Brønsted acid-catalyzed addition of 2-alkylazaarenes to in situ generated N-sulfonylimines through selective C(sp(3))-H bond functionalization has been developed. This protocol provides an atom- and step-economic approach to α-substituted sulfonamides. PMID:26868020

  13. Consecutive condensation, C-N and N-N bond formations: a copper- catalyzed one-pot three-component synthesis of 2H-indazole.


    Kumar, Manian Rajesh; Park, Ahbyeol; Park, Namjin; Lee, Sunwoo


    2H-Indazoles are synthesized using copper-catalyzed, one-pot, three-component reactions of 2-bromobenzaldehydes, primary amines, and sodium azide. A copper catalyst plays the key role in the formation of C-N and N-N bonds. This method has a broad substrate scope with a high tolerance for a variety of functional groups. PMID:21644532

  14. Ether complexes of tungsten with two different binding modes: An O-bound ether and an {eta}{sup 2}-(C=C) vinyl ether. Evidence for C-H...O hydrogen bonding of vinylic C-H groups

    SciTech Connect

    Song, J.S.; Szalda, D.J.; Bullock, R.M.


    The reaction of PhCH(OCH{sup 3}){sup 2} with Cp(CO){sup 3}WH and HOTf gives [Cp(CO){sup 3}W(PhCH{sup 2}OCH{sup 3})]{sup +}OTf{sup -}. The structure of this benzyl methyl ether complex was determined by single crystal X-ray diffraction and was shown to have the ether bonded to tungsten through the oxygen. This compound was isolated as a kinetic product of the reaction; it decomposes in solution by releasing free PhCH{sup 2}OCH{sup 3} and forming Cp(CO){sup 3}WOTf. An analog with the BAr`{sup 4}{sup -} counterion [Ar` = 3, 5-bis(trifluoromethyl)phenyl] is more stable. The reaction of the vinyl acetal CH{sup 2}=CHCH(OEt){sup 2} with Cp(CO){sup 3}WH and HOTf produces [Cp(CO){sup 3}W({eta}{sup 2}-EtOCH=CHCH{sup 3})]{sup +} OTf{sup -}, in which the ether is bonded to tungsten through the C=C bond of the vinyl ether. The crystal structure of this compound shows that the W-C(OEt) distance (2.69(3) A) is significantly longer than the W-C(CH{sup 3}) distance (2.37(3) A). There are weak C-H...O hydrogen bonds between both vinyl CH`s and oxygens of the triflate counterions. Evidence is presented that some of these weak hydrogen bonds are maintained in CD{sup 2}Cl{sup 2} solution but not in CD{sup 3}CN. 44 refs., 4 figs., 3 tabs.

  15. Rh-Catalyzed C–C Bond Cleavage by Transfer Hydroformylation

    PubMed Central

    Murphy, Stephen K.; Park, Jung-Woo; Cruz, Faben A.; Dong, Vy M.


    The dehydroformylation of aldehydes to generate olefins occurs during the biosynthesis of various sterols, including cholesterol in humans. Here, we implement a synthetic version that features the transfer of a formyl group and hydride from an aldehyde substrate to a strained olefin acceptor. A Rh(Xantphos)(benzoate) catalyst activates aldehyde C–H bonds with high chemoselectivity to trigger C–C bond cleavage and generate olefins at low loadings (0.3 to 2 mol%) and temperatures (22 to 80 °C). This mild protocol can be applied to various natural products and was used to achieve a three step synthesis of (+)-yohimbenone. A study of the mechanism reveals that the benzoate counterion acts as a proton-shuttle to enable transfer hydroformylation. PMID:25554782

  16. Nickel-catalyzed Csp2-Csp3 bond formation by carbon-fluorine activation.


    Sun, Alex D; Leung, Kaylyn; Restivo, Anita D; LaBerge, Nicole A; Takasaki, Harumi; Love, Jennifer A


    We report herein a general catalytic method for Csp(2)-Csp(3) bond formation through C-F activation. The process uses an inexpensive nickel complex with either diorganozinc or alkylzinc halide reagents, including those with β-hydrogen atoms. A variety of fluorine substitution patterns and functional groups can be readily incorporated. Sequential reactions involving different precatalysts and coupling partners permit the synthesis of densely functionalized fluorinated building blocks. PMID:24522982

  17. Boron-Catalyzed Aromatic C-H Bond Silylation with Hydrosilanes.


    Ma, Yuanhong; Wang, Baoli; Zhang, Liang; Hou, Zhaomin


    Metal-free catalytic C-H silylation of a series of aromatic compounds such as N,N-disubstituted anilines with various hydrosilanes has been achieved for the first time using commercially available B(C6F5)3 as a catalyst. This protocol features simple and neutral reaction conditions, high regioselectivity, wide substrate scope (up to 40 examples), Si-Cl bond compatibility, and no requirement for a hydrogen acceptor. PMID:26959863

  18. Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides.


    Li, Yuanming; Ma, Lina; Jia, Fan; Li, Zhiping


    A general and efficient method for amide bond synthesis has been developed. The method allows for synthesis of tertiary amides from readily available tertiary amines and anhydrides in the presence of FeCl2 as catalyst and tert-butyl hydroperoxide in water (T-Hydro) as oxidant. Mechanistic studies indicated that the in situ-generated α-amino peroxide of tertiary amine and iminium ion act as key intermediates in this oxidative transformation. PMID:23668222

  19. Sulfide synthesis through copper-catalyzed C-S bond formation under biomolecule-compatible conditions.


    Zhang, Yonghong; Li, Yiming; Zhang, Xiaomei; Jiang, Xuefeng


    We report here an efficient and mild method for constructing C-S bonds. The reactions were carried out with Na2S2O3 as a sulfurating reagent, CuSO4 as a catalyst, and water as solvent without any surfactant. The products were achieved in moderate to excellent yields at room temperature under air. Notably, this reaction is compatible with various biomolecules including amino acids, oligosaccharides, nucleosides, proteins, and cell lysates. PMID:25435202

  20. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O((3)P)+allyl radical intermediate.


    Fitzpatrick, Benjamin L; Alligood, Bridget W; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min


    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H(2)COCH)CH(2)Cl. The three dominant photoproduct channels analyzed are c-(H(2)COCH)CH(2)+Cl, c-(H(2)COCH)+CH(2)Cl, and C(3)H(4)O+HCl. In the second channel, the c-(H(2)COCH) photofission product is a higher energy intermediate on C(2)H(3)O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H(2)CCO. The final primary photodissociation pathway HCl+C(3)H(4)O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H(2)COC)=CH(2); the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C(3)H(5)O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O((3)P)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C(2)H(4) and H(2)CO+C(2)H(3) product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C(2)H(4) products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H(2)CO+C(2)H(3) product channel of the O((3)P)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from tangential recoil during the dissociation of highly rotationally excited nascent radicals formed photolytically in this

  1. Enantioselective copper-catalyzed carboetherification of unactivated alkenes.


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


    Chiral saturated oxygen heterocycles are important components of bioactive compounds. Cyclization of alcohols onto pendant alkenes is a direct route to their synthesis, but few catalytic enantioselective methods enabling cyclization onto unactivated alkenes exist. Herein reported is a highly efficient copper-catalyzed cyclization of γ-unsaturated pentenols which terminates in C-C bond formation, a net alkene carboetherification. Both intra- and intermolecular C-C bond formations are demonstrated, thus yielding functionalized chiral tetrahydrofurans as well as fused-ring and bridged-ring oxabicyclic products. Transition-state calculations support a cis-oxycupration stereochemistry-determining step. PMID:24798697

  2. C-C and C-Heteroatom Bond Dissociation Energies in CH 3 R'C(OH) 2 : Energetics for Photocatalytic Processes of Organic Diolates on TiO 2 Surfaces

    SciTech Connect

    Wang, Tsang-Hsiu; Dixon, David A.; Henderson, Michael A.


    The bond energies of a range of gem-diols, CH3R'C(OH)2 (R' = H, F, Cl, Br, CN, NO2, CF3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, ((CH3)2)CH, (CH3)3C, ((CH3)2CH)CH2, (CH3CH2)(CH3)CH, C6H5 (CH3CH2)(CH3)CH) which serve as models for binding to a surface have been studied with density functional theory (DFT) and the molecular orbital G3(MP2) methods to provide thermodynamic data for the analysis of the photochemistry of ketones on TiO2. The ultraviolet (UV) photon-induced photodecomposition of adsorbed acetone and 3,3-dimethylbutanone on the rutile TiO2 (110) surface have been investigated with photon stimulated desorption (PSD) and temperature programmed desorption (TPD). The C-CH3 and C-C(R') bond dissociation energies in CH3R'C(OH)2 were predicted, and our calculated bond dissociation energies are in excellent agreement with the available experimental values. We used a series of isodemic reactions to provide small corrections to the various bond dissociation energies. The calculated bond dissociation energies are in agreement with the observed photodissociation processes except for R' = CF3, suggesting that these processes are under thermodynamic control. For R' = CF3, reaction dynamics also play a role in determining the photodissociation mechanism. The gas phase Brönsted acidities of the gem-diols were calculated. For three molecules, R' = Cl, Br, and NO2, loss of a proton leads to the formation of a complex of acetic acid with the anion Cl-, Br-, and NO2-. The acidities of these three species are very high with the former two having acidities comparable to CF3SO3H. The ketones (R'RC(=O)) are weak Lewis acids except where addition of OH- leads to the dissociation of the complex to form an anion bonded to acetic acid, R' = NO2, Cl, and Br. The X-C bond dissociation energies for a number of X-CO2- species were calculated and these should be useful in correlating with photochemical reactivity studies.

  3. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O({sup 3}P)+allyl radical intermediate

    SciTech Connect

    FitzPatrick, Benjamin L.; Alligood, Bridget W.; Butler, Laurie J.; Lee, Shih-Huang; Lin, Jim Jr-Min


    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H{sub 2}COCH)CH{sub 2}Cl. The three dominant photoproduct channels analyzed are c-(H{sub 2}COCH)CH{sub 2}+Cl, c-(H{sub 2}COCH)+CH{sub 2}Cl, and C{sub 3}H{sub 4}O+HCl. In the second channel, the c-(H{sub 2}COCH) photofission product is a higher energy intermediate on C{sub 2}H{sub 3}O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H{sub 2}CCO. The final primary photodissociation pathway HCl+C{sub 3}H{sub 4}O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H{sub 2}COC)=CH{sub 2}; the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C{sub 3}H{sub 5}O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O({sup 3}P)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C{sub 2}H{sub 4} and H{sub 2}CO+C{sub 2}H{sub 3} product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C{sub 2}H{sub 4} products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H{sub 2}CO+C{sub 2}H{sub 3} product channel of the O({sup 3}P)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from

  4. Molecular mechanism of acid-catalyzed hydrolysis of peptide bonds using a model compound.


    Pan, Bin; Ricci, Margaret S; Trout, Bernhardt L


    The stability of peptide bonds is a critical aspect of biological chemistry and therapeutic protein applications. Recent studies found elevated nonenzymatic hydrolysis in the hinge region of antibody molecules, but no mechanism was identified. As a first step in providing a mechanistic interpretation, this computational study examines the rate-determining step of the hydrolytic reaction of a peptide bond under acidic pH by a path sampling technique using a model compound N-MAA. Most previous computational studies did not include explicit water molecules, whose effects are significant in solution chemistry, nor did they provide a dynamic picture for the reaction process in aqueous conditions. Because no single trajectory can be used to describe the reaction dynamics due to fluctuations at finite temperatures, a variant version of the transition path sampling technique, the aimless shooting algorithm, was used to sample dynamic trajectories and to generate an ensemble of transition trajectories according to their statistical weights in the trajectory space. Each trajectory was computed as the time evolution of the molecular system using the Car-Parrinello molecular dynamics technique. The likelihood maximization procedure and its modification were used in extracting dynamically relevant degrees of freedom in the system, and approximations of the reaction coordinate were compared. Its low log-likelihood score and poor p(B) histogram indicate that the C-O distance previously assumed as the reaction coordinate for the rate-determining step is inadequate in describing the dynamics of the reaction. More than one order parameter in a candidate set including millions of geometric quantities was required to produce a convergent reaction coordinate model; its involvement of many degrees of freedom suggests that this hydrolytic reaction step is very complex. In addition to affecting atoms directly involved in bond-making and -breaking processes, the water network also has

  5. Copper-Carbene Intermediates in the Copper-Catalyzed Functionalization of O-H Bonds.


    Pereira, Ana; Champouret, Yohan; Martín, Carmen; Álvarez, Eleuterio; Etienne, Michel; Belderraín, Tomás R; Pérez, Pedro J


    Copper-carbene [Tp(x)Cu=C(Ph)(CO2Et)] and copper-diazo adducts [Tp(x)Cu{η(1)-N2C(Ph)(CO2Et)}] have been detected and characterized in the context of the catalytic functionalization of O-H bonds through carbene insertion by using N2=C(Ph)(CO2Et) as the carbene source. These are the first examples of these type of complexes in which the copper center bears a tridentate ligand and displays a tetrahedral geometry. The relevance of these complexes in the catalytic cycle has been assessed by NMR spectroscopy, and kinetic studies have demonstrated that the N-bound diazo adduct is a dormant species and is not en route to the formation of the copper-carbene intermediate. PMID:26014686

  6. B-N, B-O, and B-CN Bond Formation via Palladium-Catalyzed Cross-Coupling of B-Bromo-Carboranes.


    Dziedzic, Rafal M; Saleh, Liban M A; Axtell, Jonathan C; Martin, Joshua L; Stevens, Simone L; Royappa, A Timothy; Rheingold, Arnold L; Spokoyny, Alexander M


    Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters. PMID:27384544

  7. Base-Catalyzed Insertion of Dioxygen into Rhodium-Hydrogen Bonds: Kinetics and Mechanism

    SciTech Connect

    Szajna-Fuller, Ewa; Bakac, Andreja


    The reaction between molecular oxygenm and rhodium hydrides L(OH)RhH{sup +} (L = (NH{sub 3}){sub 4}, trans-L{sup 1}, and cis-L{sup 1}, where L{sup 1} = cyclam) in basic aqueous solutions rapidly produces the corresponding hydroperoxo complexes. Over the pH range 8 < pH < 12, the kinetics exhibit a first order dependence on [OH{sup -}]. The dependence on [O{sub 2}] is less than first order and approaches saturation at the highest concentrations used. These data suggest an attack by OH{sup -} at the hydride with k = (1.45 {+-} 0.25) x 10{sup 3} M{sup -1} s{sup -1} for trans-L{sup 1}(OH)RhH{sup +} at 25 C, resulting in heterolytic cleavage of the Rh-H bond and formation of a reactive Rh(I) intermediate. A competition between O{sub 2} H{sub 2}O for Rh(I) is the source of the observed dependence on O{sub 2}.

  8. The role of ammonization on chemical bonding and optical properties of nickel-catalyzed gallium nitride nanowire

    NASA Astrophysics Data System (ADS)

    Rizal, Umesh; Swain, Bhabani S.; Swain, Bibhu P.


    Nickel-catalyzed gallium nitride nanowires (GaN-NWs) were grown on p-type Si (100) substrates using Ga2O3 powder and NH3, N2, and H2 as precursor gases in chemical vapor deposition reactor. The GaN-NWs were characterized by atomic force microscopy (AFM), Fourier transform infrared spectroscopy, Raman spectroscopy, and photoluminescence (PL) spectroscopy to investigate microstructural, structural, optical, and chemical bonding networks of GaN-NW films. AFM shows the formation of GaN-NWs with different diameter. The room temperature PL spectra of GaN-NWs show a broad blue emission band centered at 2.54, 2.69, 2.81, 2.89, and 2.94 eV, which are associated with different electronic transitions. The stokes shift of GaN-NWs reveals the existence of prominent transverse optic and longitudinal optic (LO) peak at 548 and 795 cm-1, respectively. However, the pronounced blue shifting of LO peak was observed with increasing NH3 flow rate indicates considerable stress in NWs.

  9. Unique Reactivity Patterns Catalyzed by Internal Lewis Acid Assisted Hydrogen Bond Donors

    NASA Astrophysics Data System (ADS)

    Auvil, Tyler Jay

    The advancement of hydrogen bond donor (HBD) organocatalysis has been inhibited by a number of challenges. Conventional HBDs suffer from high catalyst loadings and operate in only limited types of reactions, typically the activation of 1,2- and 1,4-acceptors for nucleophilic attack. One strategy to address the shortcomings of HBD catalysis is to design innovative catalysts with improved reactivity. To this end, boronate ureas have been developed as a new family of enhanced HBD catalysts that enable useful new reactivity patterns. Boronate ureas are easily-accessible, small organic molecules that benefit from improved catalytic abilities plausibly due to internal coordination of the urea carbonyl to a strategically placed Lewis acid. Optimization of the boronate urea scaffold has revealed their enhanced catalytic activity, enabling new directions in HBD catalysis. The discovery of boronate ureas has allowed for the unveiling of new HBD activation modes, providing unique reactivity patterns that are inaccessible with conventional HBD catalysts. Among these reactivity patterns is the activation of strained nitrocyclopropane carboxylates for nucleophilic ring-opening reactions, which affords a swift route to access gamma-amino-alpha-nitroester building blocks. The ring-opening method was highlighted by its utilization in the total synthesis of a CB-1 receptor inverse agonist, which was recently patented by Eli Lilly. Additionally, boronate ureas can elicit carbene-like reactivity from alpha-diazocarbonyl compounds, allowing for organocatalytic heteroatom-hydrogen insertions reactions, the first of their kind. The boronate urea activation of alpha-nitrodiazoesters has permitted the development of an unsymmetric double alpha-arylation process, affording a synthetically challenging motif in a single flask. The alpha-arylation reaction proceeds through a conceptually novel organocatalytic transient N--H insertion process, employing anilines as carbene activators. The use

  10. Iron-Carbonyl-Catalyzed Redox-Neutral [4+2] Annulation of N-H Imines and Internal Alkynes by C-H Bond Activation.


    Jia, Teng; Zhao, Chongyang; He, Ruoyu; Chen, Hui; Wang, Congyang


    Stoichiometric C-H bond activation of arenes mediated by iron carbonyls was reported by Pauson as early as in 1965, yet the catalytic C-H transformations have not been developed. Herein, an iron-catalyzed annulation of N-H imines and internal alkynes to furnish cis-3,4-dihydroisoquinolines is described, and represents the first iron-carbonyl-catalyzed C-H activation reaction of arenes. Remarkablely, this is also the first redox-neutral [4+2] annulation of imines and alkynes proceeding by C-H activation. The reaction also features only cis stereoselectivity and excellent atom economy as neither base, nor external ligand, nor additive is required. Experimental and theoretical studies reveal an oxidative addition mechanism for C-H bond activation to afford a dinuclear ferracycle and a synergetic diiron-promoted H-transfer to the alkyne as the turnover-determining step. PMID:27002210