Download or read book Mechanistic Insights Into Copper Catalyzed Sp3 C H Functionalization written by Eun Sil Jang and published by . This book was released on 2015 with total page 394 pages. Available in PDF, EPUB and Kindle. Book excerpt: Herein we describe the mechanistic understanding of -diketiminato copper(I) complexes, [CuI], in catalytic intramolecular sp3 C-H functionalization using tBuOOtBu as an oxidant. With initial success in C-H amination using unactivated alkyl and arylamines, H-NR1R2, each step in the proposed catalytic cycle underwent rigorous analysis, largely devoted to understanding the role of -diketiminato copper(II) amide intermediates [CuII]-NR1R2. Previous studies proposed [CuII]-NHAd (Ad = adamantyl) as the intermediate responsible for a key step in our catalysis, capable of performing both hydrogen atom abstraction (HAA) of R-H to give R as well as radical capture (RC) of this alkyl radical R to give R-NHAd and [CuI]. With other copper(II) amides bearing aromatic N-substituents, the role of such [CuII]-NHAr species is primarily to capture the R radical formed via HAA of R-H by •OtBu (released by [CuI] catalyzed homolytic cleavage of tBuOOtBu). This amino variant Kharasch-Sosnovsky reaction has been effectively applied to other functional groups such as alcohols, nitroalkanes, and aryl ketones to introduce new methods for sp3-C-O and sp3-sp3 C-C bond formation.

Download or read book Oxidative Cross Coupling Reactions written by Aiwen Lei and published by John Wiley & Sons. This book was released on 2016-08-12 with total page 240 pages. Available in PDF, EPUB and Kindle. Book excerpt: The first handbook on this emerging field provides a comprehensive overview of transition metal-catalyzed coupling reactions in the presence of an oxidant. Following an introduction to the general concept and mechanism of this reaction class, the team of authors presents chapters on C-C cross-coupling reactions using organometallic partners, C-Heteroatom bond forming reactions via oxidative couplings, and C-H couplings via C-H activation. The text also covers such groundbreaking topics as recent achievements in the fields of C-C and C-X bond formation reactions as well as C-H activation involving oxidative couplings. With its novel and concise approach towards important building blocks in organic chemistry and its focus on synthetic applications, this handbook is of great interest to all synthetic chemists in academia and industry alike.

Download or read book Mechanistic Studies on Transition Metal Catalyzed C H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods written by Gui-Juan Cheng and published by Springer. This book was released on 2017-06-07 with total page 140 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction. The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.

Download or read book Radical Strategies for hetero benzylic C sp3 H Functionalization and Cross Coupling written by Dung Le Golden and published by . This book was released on 2023 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: C-H functionalization reactions are among the most useful and synthetically applicable approaches to access structurally complex organic molecules, including pharmaceuticals and agrochemicals. While methods promoting functionalization and cross coupling of C(sp2)-H bonds have found broad applications, a growing number of reactions have focused on functionalizing C(sp3)-H bonds to incorporate three-dimensionality and expand the chemical space. Radical C-H functionalization reactions initiated by hydrogen-atom transfer and proceeding via radical intermediates introduce strategic opportunities to functionalize C(sp3)-H bonds. In addition to the commonly seen radical-chain and biomimetic radical-rebound mechanisms, radical-relay reactions provide the basis for versatile C-H cross-coupling methods with diverse partners. This thesis discloses our recent development of radical-relay and radical-chain (hetero)benzylic C(sp3)-H functionalization and their synthetic utility in accessing three-dimensional chemical space. Chapter 2 discussed our recent development of a copper-catalyzed benzylic C-H esterification reaction enabled by a "photochemical redox buffering" strategy using tert-butyl peroxybenzoate as the oxidant. Copper(I)/peroxide (or Kharasch-Sosnovsky-typed) reactions historically require excess of C-H substrates and forcing reaction conditions, leading to poor synthetic applicability. Copper(I) catalysts interact rapidly with peroxide-based oxidants, resulting in a pool of inactive copper(II) species, which are incapable of activating oxidants. Our recent efforts in copper/NFSI-catalyzed radical relay functionalization and cross coupling of benzylic C(sp3)-H bonds revealed a ''redox buffering'' strategy enabling the controlled regeneration of copper(I). For copper/NFSI systems, we have identified that certain nucleophiles (i.e. cyanides and arylboronic acids) can promote the reduction of CuII to CuI, whereas nucleophiles like alcohols and azoles requires additional chemical reductants (i.e. dialkylphosphites) to promote ''redox buffering.'' To address the issues with copper/peroxide system, we have developed a 2,2'-biquinoline/copper-catalyzed reaction under photoirradiation to promote benzylic esterification using limiting C-H substrates. Mechanistic interrogation revealed that light promoted carboxylate-to-copper charge transfer enables the regeneration of copper(I) catalyst, similar to the aforementioned ''redox buffering'' approach. Chapter 3 disclosed our recently developed chlorination/ diversification sequence of heterobenzylic C(sp3)-H bonds in 3-alkylpyridines via radical chain. Alkylpyridines are important and prevalent classes of substrates in medicinal chemistry with the (hetero)benzylic C-H bonds having similar bond dissociation energies to alkylarenes. However, copper/NFSI-catalyzed reactions are unsuccessful in accessing these C-H bonds due to the deleterious reactivity between the pyridyl nitrogen atom and NFSI. While chlorination of 2- and 4-alkylpyridines can be achieved using a polar activation strategy, heterobenzylic C-H bonds of 3-alkylpyridines are more amenable to radical-based chlorination. Experimental and density functional theory identified an N-chlorosulfonamide reagent for selective chlorination at the heterobenzylic C-H site. Subsequent diversification of heterobenzyl chlorides with a broad scope of nucleophiles enabled facile access to complex cross-coupled products. This method should find broad application for building block modification and library synthesis in drug discovery. Chapter 4 detailed our investigation in copper/NFSI-catalyzed fluorination of benzylic C-H bonds followed by diversification with various nucleophiles. Redox buffering promoted by addition of boron-based reductants enabled successful fluorination with limiting C-H substrates. Benzyl fluorides were subsequently subjected to nucleophilic displacement catalyzed by Lewis acidic additives, affording C-O, C-N, and C-C bond formations. This method inspired later developments of other radical halogenation/diversification methods to functionalize (hetero)benzylic C-H bonds. Chapter 5 disclosed our development of a copper/NFSI-catalyzed cross couplings of benzylic C(sp3)-H bonds and azoles enabled by redox buffering. In addition to excellent benzylic selectivity, N-site selectivity of azoles was achieved by modifying the reaction conditions. Diverse N-H heterocycles were compatible coupling partners, including pyrazoles, purines, and sultams. The ability to access both regioisomers of azoles via a cross coupling array validated the synthetic utility of this method in pharmaceutical research. Collectively, radical (hetero)benzylic C(sp3)-H functionalization contributed to a growing number of methods in accessing more three-dimensional chemical space. Mechanistic insights from these reactions will enable further development of more synthetically useful methodologies. Additionally, the synthetic applications should allow chemists to assemble compound libraries with higher complexity and expand the accessible chemical space.

Download or read book Iron and Cobalt Catalysts written by Wilson D. Shafer and published by MDPI. This book was released on 2020-06-23 with total page 414 pages. Available in PDF, EPUB and Kindle. Book excerpt: Since the turn of the last century when the field of catalysis was born, iron and cobalt have been key players in numerous catalysis processes. These metals, due to their ability to activate CO and CH, haev a major economic impact worldwide. Several industrial processes and synthetic routes use these metals: biomass-to-liquids (BTL), coal-to-liquids (CTL), natural gas-to-liquids (GTL), water-gas-shift, alcohol synthesis, alcohol steam reforming, polymerization processes, cross-coupling reactions, and photocatalyst activated reactions. A vast number of materials are produced from these processes, including oil, lubricants, waxes, diesel and jet fuels, hydrogen (e.g., fuel cell applications), gasoline, rubbers, plastics, alcohols, pharmaceuticals, agrochemicals, feed-stock chemicals, and other alternative materials. However, given the true complexities of the variables involved in these processes, many key mechanistic issues are still not fully defined or understood. This Special Issue of Catalysis will be a collaborative effort to combine current catalysis research on these metals from experimental and theoretical perspectives on both heterogeneous and homogeneous catalysts. We welcome contributions from the catalysis community on catalyst characterization, kinetics, reaction mechanism, reactor development, theoretical modeling, and surface science.

Download or read book Copper Mediated Cross Coupling Reactions written by Gwilherm Evano and published by John Wiley & Sons. This book was released on 2013-09-23 with total page 682 pages. Available in PDF, EPUB and Kindle. Book excerpt: Providing comprehensive insight into the use of copper in cross-coupling reactions, Copper-Mediated Cross-Coupling Reactions provides a complete up-to-date collection of the available reactions and catalytic systems for the formation of carbon-heteroatom and carbon-carbon bonds. This essential reference covers a broad scope of copper-mediated reactions, their variations, key advances, improvements, and an array of academic and industrial applications that have revolutionized the field of organic synthesis. The text also discusses the mechanism of these transformations, the use of copper as cost-efficient alternative to palladium, as well as recently developed methods for conducting copper-mediated reactions with supported catalysts.

Download or read book Copper Catalysis in Organic Synthesis written by Gopinathan Anilkumar and published by John Wiley & Sons. This book was released on 2020-12-07 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: The most current information on growing field of copper catalysis Copper Catalysis in Organic Synthesis contains an up-to-date overview of the most important reactions in the presence of copper catalysts. The contributors—noted experts on the topic—provide an introduction to the field of copper catalysis, reviewing its development, scope, and limitations, as well as providing descriptions of various homo- and cross-coupling reactions. In addition, information is presented on copper-catalyzed C–H activation, amination, carbonylation, trifluoromethylation, cyanation, and click reactions. Comprehensive in scope, the book also describes microwave-assisted and multi-component transformations as well as copper-catalyzed reactions in green solvents and continuous flow reactors. The authors highlight the application of copper catalysis in asymmetric synthesis and total synthesis of natural products and heterocycles as well as nanocatalysis. This important book: Examines copper and its use in organic synthesis as a more cost-effective and sustainable for researchers in academia and industry Offers the first up-to-date book to explore copper as a first line catalyst for many organic reactions Presents the most significant developments in the area, including cross-coupling reactions, C–H activation, asymmetric synthesis, and total synthesis of natural products and heterocycles Contains over 20 contributions from leaders in the field Written for catalytic chemists, organic chemists, natural products chemists, pharmaceutical chemists, and chemists in industry, Copper Catalysis in Organic Synthesis offers a book on the growing field of copper catalysis, covering cross-coupling reactions, C–H activation, and applications in the total synthesis of natural products.

Download or read book Organic Reaction Mechanisms 2013 written by A. C. Knipe and published by John Wiley & Sons. This book was released on 2016-10-31 with total page 728 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic Reaction Mechanisms 2013, the 49th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2013. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular Rearrangements An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.

Download or read book Mechanistic Studies of Copper and Nickel Catalyzed Sp3 C H Functionalization written by Abolghasem Bakhoda and published by . This book was released on 2019 with total page 516 pages. Available in PDF, EPUB and Kindle. Book excerpt: Recent studies from our laboratory have discovered that C−H functionalization with unactivated amines, anilines or acyl−protected phenols with tBuOOtBu as an oxidant can take place at CuI b−diketiminates under a radical−relay mechanism. Mechanistic studies revealed that while in some cases the copper(II) alkylamide [CuII]−NHR' is capable of HAA, the principle role of the copper intermediates [CuII]−NHR' or [CuII]−OAr is to capture an alkyl radical R• (generated in the HAT of R−H substrate via tBuO• radical) to form R−NHR' or R'OAr, respectively.

Download or read book Organic Reaction Mechanisms 2018 written by Mark G. Moloney and published by John Wiley & Sons. This book was released on 2021-08-17 with total page 692 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic Reaction Mechanisms 2018, the 54th annual volume in this highly successful and unique series, surveys research on organic reaction mechanisms described in the available literature dated 2018. The following classes of organic reaction mechanisms are comprehensively reviewed: Reaction of Aldehydes and Ketones and their Derivatives Reactions of Carboxylic, Phosphoric, and Sulfonic Acids and their Derivatives Oxidation and Reduction Carbenes and Nitrenes Nucleophilic Aromatic Substitution Electrophilic Aromatic Substitution Carbocations Nucleophilic Aliphatic Substitution Carbanions and Electrophilic Aliphatic Substitution Elimination Reactions Polar Addition Reactions Cycloaddition Reactions Molecular Rearrangements Transition Metal Coupling Radical Reactions An experienced team of authors compile these reviews every year, so that the reader can rely on a continuing quality of selection and presentation.

Download or read book C H Bond Activation and Catalytic Functionalization I written by Pierre H. Dixneuf and published by Springer. This book was released on 2015-12-18 with total page 269 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Topics in Organometallic Chemistry presents critical overviews of research results in organometallic chemistry. As our understanding of organometallic structure, properties and mechanisms increases, new ways are opened for the design of organometallic compounds and reactions tailored to the needs of such diverse areas as organic synthesis, medical research, biology and materials science. Thus the scope of coverage includes a broad range of topics of pure and applied organometallic chemistry, where new breakthroughs are being achieved that are of significance to a larger scientific audience. The individual volumes of Topics in Organometallic Chemistry are thematic. Review articles are generally invited by the volume editors. All chapters from Topics in Organometallic Chemistry are published OnlineFirst with an individual DOI. In references, Topics in Organometallic Chemistry is abbreviated as Top Organomet Chem and cited as a journal.

Download or read book Advances in Organometallic Chemistry written by and published by Academic Press. This book was released on 2016-10-21 with total page 300 pages. Available in PDF, EPUB and Kindle. Book excerpt: Advances in Organometallic Chemistry contains authoritative review articles of worldwide known researchers on the field of organometallic chemistry, covering topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. The book will benefit a wide range of researchers involved in organometallic chemistry, including synthetic protocols, mechanistic studies, and practical applications. Contains contributions from leading authorities in the field of organometallic chemistry Covers topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more Informs and updates readers on all the latest developments in the field Carefully edited to provide easy-to-read material

Download or read book Asymmetric Functionalization of C H Bonds written by Shu-Li You and published by Royal Society of Chemistry. This book was released on 2015-08-13 with total page 433 pages. Available in PDF, EPUB and Kindle. Book excerpt: Asymmetric C-H direct functionalization reactions are one of the most active and fascinating areas of research in organic chemistry due to their significance in the construction of molecular complexity without pre-activation, and the step economy and atom economy features in potential synthetic application. Distinguishing the reactivity among numerous C–H bonds in one single molecule represents one of the most challenging issues in organic synthesis and requires precise reaction design. As such, this field is now receiving increasing attention from researchers. This book provides the first comprehensive review of this field, summarizing the origin, mechanism, scope and applications of the asymmetric C-H bond functionalization reaction. It covers organocatalytic reactions and transition-metal-catalyzed reactions, as well as asymmetric C-H functionalization reactions not described in other books. Written by a leading expert in this field, the book is ideal for postgraduates and researchers working in organic synthesis, catalysis, and organometallic chemistry.

Download or read book Strategies for Palladium Catalyzed Non directed and Directed C bond H Bond Functionalization written by Anant R. Kapdi and published by Elsevier. This book was released on 2017-05-23 with total page 502 pages. Available in PDF, EPUB and Kindle. Book excerpt: Strategies for Palladium-Catalyzed Non-directed and Directed C-H Bond Functionalization portrays the complete scope of these two aspects of C-H bond functionalization in a single volume for the first time. Featured topics include the influence of palladacyclic systems in C-H bond functionalization (need for newer catalytic systems for better efficiency), mechanistic aspect of the functionalization strategies leading to better systems, and applications of these methodologies to natural product synthesis and material synthesis. Addresses the involvement of catalytic systems (palladacycles) for better functionalization of (hetero)arenes to emphasize the need for developing better, more selective systems Covers the use of powerful mechanistic tools for understanding and assisting the development of better functionalization strategies Discusses the finer aspects of C-H bond functionalization, such as control of regioselectivity with or without directing groups Includes a chapter detailing the synthesis of naturally occurring molecules or functional molecules via both pathways for assessing the applicability of the functionalization strategies

Download or read book Chemical Photocatalysis written by Burkhard König and published by Walter de Gruyter GmbH & Co KG. This book was released on 2020-04-06 with total page 531 pages. Available in PDF, EPUB and Kindle. Book excerpt: Visible light is an abundant source of energy. While the conversion of light energy into electrical energy (photovoltaics) is highly developed and commercialized, the use of visible light in chemical synthesis is far less explored. Chemical photocatalysts that mimic principles of biological photosynthesis utilize visible light to drive endothermic or kinetically hindered reactions.

Download or read book Transition Metal Catalyzed C H Functionalization of Heterocycles 2 Volumes written by Tharmalingam Punniyamurthy and published by John Wiley & Sons. This book was released on 2023-03-28 with total page 1209 pages. Available in PDF, EPUB and Kindle. Book excerpt: Transition-Metal-Catalyzed C-H Functionalization of Heterocycles A comprehensive guide to recent advances in this field Constituting the majority of all known compounds, heterocycles are structures that incorporate one or more heteroatoms within their core, thus exhibiting properties that are quite different from their all-carbon analogs. They are fundamental to all fields of chemistry and, therefore, their synthesis and modification has attracted a great deal of attention in the recent years. In this vein, transition-metal-catalyzed C-H bond functionalization forms a crucial tool for generating and analyzing heterocyclic compounds. Transition-Metal-Catalyzed C-H Functionalization of Heterocycles, Two-Volume Set, showcases diverse C-H functionalization methodologies and their incorporation into the latest research. The chapters serve as an essential tool depicting detailed site-selective functionalization of heterocyclic cores, along with a comprehensive discussion on their mechanistic approaches. Readers of Transition-Metal-Catalyzed C-H Functionalization of Heterocycles, Two-Volume-Set will also find: A detailed introduction to C-H activation along with the mechanistic aspects of transition-metal-catalyzed C-H bond activation reactions Easy-to-use structures with each chapter dedicated to a type of heterocycle and its specific functionalization methodologies A leading team of international authors in C-H bond functionalization Transition-Metal-Catalyzed C-H Functionalization of Heterocycles, Two-Volume-Set is a valuable guide for students and researchers in organic synthesis and process development, in both academic and industrial contexts.

Download or read book Advances in Organometallic Chemistry written by Pedro J. Perez and published by Academic Press. This book was released on 2021-06-17 with total page 272 pages. Available in PDF, EPUB and Kindle. Book excerpt: Advances in Organometallic Chemistry, Volume 76, the latest release in this longstanding serial is known for its comprehensive coverage of topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more. It is ideal for a wide range of researchers involved in organometallic chemistry, including synthetic protocols, mechanistic studies and practical applications. Contains contributions from leading authorities in the field of organometallic chemistry Covers topics in organometallic synthesis, reactions, mechanisms, homogeneous catalysis, and more Informs and updates readers on the latest developments in the field Carefully edited to provide easy-to-read material