Nickel And Cobalt Catalyzed Hydrofunctionalization Reaction Of Alkene
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Nickel And Cobalt Catalyzed Hydrofunctionalization Reaction Of Alkene
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Author : Balaram Raya
language : en
Publisher:
Release Date : 2016
Nickel And Cobalt Catalyzed Hydrofunctionalization Reaction Of Alkene written by Balaram Raya and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2016 with categories.
Organic reactions catalyzed by metal complexes are an effective way to improve atom economy and environmental friendliness for many synthetic transformations. Among the various synthetic transformations, hydrosilylation reaction has huge industrial applications for manufacturing consumer goods. The alkylsilanes from alkene hydrosilylation are widely used as raw materials in manufacturing silicon rubbers, molding implants and adhesive. The hydrosilylation reactions can also produce various organosilicon reagents, which are used in fine chemical synthesis for stereospecific oxidation and cross coupling reaction. Over the long decades, numerous reports on metal-catalyzed hydrosilylations include the use of platinum, palladium, rhodium, ruthenium, iridium, lanthanides and actinides, early transition metals, iron, cobalt to a limited extent nickel. This work has shown that readily accessible (iPrPDI)CoCl2 reacts with 2 equivalents NaEt3BH at -78 oC in toluene to generate a catalyst that effects highlyselective anti-Markovnikov hydrosilylation of the terminal double bond in alkene, 1,3- and 1,4-dienes. Primary and secondary silanes such as PhSiH3, Ph2SiH2 and PhSi(Me)H2 react with a broad spectrum of dienes without affecting the configuration of the other double bond. A slight modification of the reaction conditions using a less reactive silane (OEt)2Si(Me)H leads to unprecedented and highly selective reduction of the terminal double bond with no contamination from the silane or reduction products of the more substituted double bond. The major limitation for cobalt catalyzed hydrosilylation reaction using redox active PDI ligand is its terminal selectivity. However, this active catalyst did not work for 1,1-disubstituted alkenes. In this connection, we also observed efficient cobalt catalyst system for hydrosilylation of 1,1-disubstituted alkenes using chelating phosphine ligand at room temperature, which is able to do hydrosilylation for numerous substrates such as alkene, vinyl arene, conjugated diene, 1,4-skipped diene and 1,1-disubstituted alkenes. Carbocyclizations of a,¿-p-systems are extremely important and useful reactions for the synthesis of a variety of carbocyclic and heterocyclic compounds. Although metal catalyzed cyclization has been long known, controlling the selectivity (chemo- and regio-) remains an important challenge in this field. Nickel complexes have been known to be specifically effective for cyclic homo-and co-oligomerization of alkenes, alkynes and dienes. During the past few years, through an approach that relied mostly on mechanistic insights and systematic examination of ligand effects, RajanBabu group has discovered a number of protocols for Ni(II)-catalyzed heterodimerization reactions of vinylarenes, selected 1,3-dienes and strained olefins. Substitution of one of the phenyl groups of triphenylphosphine with a 2-benzyloxy-(e.g., L18), 2-benzyloxy-methyl-(L19) or 2-benzyloxyethyl-(L20) phenyl moiety results in a set of simple ligands, which exhibit strikingly different behavior in various nickel (II)-catalyzed olefin dimerization reactions including related cycloisomerization of 1,6-dienes. Nickel(II)-catalyzed cycloisomerization of 1,6-dienes into methylenecyclopentanes, a reaction mechanistically related to the other heterodimerization reactions, is also uniquely affected by nickel(II) complexes of L18, but not of L19 or L20. In an attempt to prepare authentic samples of the methylenecyclohexane products, nickel(II) complexes of N-heterocyclic carbene ligands were examined. In contrast to the phosphine, which gives the methylenecyclopentanes, methylenecyclohexanes are the major products in the N-heterocyclic carbine ligated nickel (II)-mediated reaction. This dissertation discusses the ligand effect on hydrofuctionalization of alkenes using nickel or cobalt metal complexes.
Evaluation Of K4 Diimine Nickel And Cobalt Hydrofunctionalization Catalysts
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Author : Christopher L. Rock
language : en
Publisher:
Release Date : 2018
Evaluation Of K4 Diimine Nickel And Cobalt Hydrofunctionalization Catalysts written by Christopher L. Rock and has been published by this book supported file pdf, txt, epub, kindle and other format this book has been release on 2018 with Catalysis categories.
The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the metal centre, while the redox non-innocent core helps to overcome the one electron chemistry that is prevalent in first row transition metals. This dissertation focuses on the use of Ph2PPrDI, which can adopt a k4-configuration when bound to a metal. One reaction that is industrially useful is hydrosilylation, which allows for the preparation of silicones that are useful in the lubrication, adhesive, and cosmetics industries. Typically, this reaction relies on highly active, platinum-based catalysts. However, the high cost of this metal has inspired the search for base metal replacements. In Chapter One, an overview of existing alkene and carbonyl hydrosilylation catalysts is presented. Chapter Two focuses on exploring the reactivity of (Ph2PPrDI)Ni towards carbonyl hydrosilylation, as well as the development of the 2nd generation catalysts, (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. Chapter Three presents a new C-O bond hydrosilylation reaction for the formation of silyl esters. It was found the (Ph2PPrDI)Ni is the most active catalyst in the literature for this transformation, with turnover frequencies of up to 900 h-1. Chapter Four explores the activity and selectivity of (Ph2PPrDI)Ni for alkene hydrosilylation, including the first large scope of gem-olefins for a nickel-based catalyst. Chapter Five explores the chemistry of (Ph2PPrDI)CoH, first through electronic structure determinations and crystallography, followed by an investigation of its reactivity towards alkyne hydroboration and nitrile dihydroboration. (Ph2PPrDI)CoH is the first reported cobalt nitrile dihydroboration catalyst.
Iron Catalysed Hydrofunctionalisation Of Alkenes And Alkynes
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Author : Mark Greenhalgh
language : en
Publisher: Springer
Release Date : 2018-05-27
Iron Catalysed Hydrofunctionalisation Of Alkenes And Alkynes written by Mark Greenhalgh and has been published by Springer this book supported file pdf, txt, epub, kindle and other format this book has been release on 2018-05-27 with Science categories.
This thesis gives a thorough account of the development of iron-catalysed hydrosilylation, hydroboration and hydromagnesiation reactions. With extraordinary referencing and scientific argument, Mark Greenhalgh describes the development of methodologies which require only commercially available materials and non-specialised techniques. The intention of this approach is to ensure the science can be adopted widely by the chemical community. In addition to an insight into the processes involved in methodology development, Greenhalgh discusses and determines the relevant reaction mechanisms. This thesis provides not only the most thorough review of the area, but offers a level of insight well beyond that expected from a Ph.D. student. The work in this thesis has been published at the highest level, and the results and ideas have led to 3 industry-funded Ph.D. studentships and grant income in excess of £1 million.
Iron Catalysis Design And Applications
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Author : Jose M Palomo
language : en
Publisher: World Scientific
Release Date : 2021-03-15
Iron Catalysis Design And Applications written by Jose M Palomo and has been published by World Scientific this book supported file pdf, txt, epub, kindle and other format this book has been release on 2021-03-15 with Science categories.
Iron Catalysis: Design and Applications is an exciting new book that takes readers inside the world of iron catalysis guided by international catalysis expert, Dr Jose M Palomo. Iron is the most abundant metal in the planet, cost-effective, environmentally friendly, with an easily manipulated remediation process. In the last few years the use of this nonprecious metal has gained extraordinary attention particularly for its potential as a catalyst in different areas. This book compiles a series of chapters describing the most significant advances in the last few years since the design of different iron catalysts and nanocatalysts and iron-containing artificial and natural enzymes. The chapters also cover its application in different areas of interest such as organic synthesis, environmental remediation, enzyme-like activities or the creation of novel types of electrodes for battery design.
Cobalt Catalysis In Organic Synthesis
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Author : Marko Hapke
language : en
Publisher: John Wiley & Sons
Release Date : 2020-04-06
Cobalt Catalysis In Organic Synthesis written by Marko Hapke and has been published by John Wiley & Sons this book supported file pdf, txt, epub, kindle and other format this book has been release on 2020-04-06 with Technology & Engineering categories.
Provides a much-needed account of the formidable "cobalt rush" in organic synthesis and catalysis Over the past few decades, cobalt has turned into one of the most promising metals for use in catalytic reactions, with important applications in the efficient and selective synthesis of natural products, pharmaceuticals, and new materials. Cobalt Catalysis in Organic Synthesis: Methods and Reactions provides a unique overview of cobalt-catalysed and -mediated reactions applied in modern organic synthesis. It covers a broad range of homogeneous reactions, like cobalt-catalysed hydrogenation, hydrofunctionalization, cycloaddition reactions, C-H functionalization, as well as radical and biomimetic reactions. First comprehensive book on this rapidly evolving research area Covers a broad range of homogeneous reactions, such as C-H activation, cross-coupling, synthesis of heterocyclic compounds (Pauson-Khand), and more Chapters on low-valent cobalt complexes as catalysts in coupling reactions, and enantioselective cobalt-catalyzed transformations are also included Can be used as a supplementary reader in courses of advanced organic synthesis and organometallic chemistry Cobalt Catalysis in Organic Synthesis is an ideal book for graduates and researchers in academia and industry working in the field of synthetic organic chemistry, catalysis, organometallic chemistry, and natural product synthesis.
Synthesis And Applications In Chemistry And Materials In 4 Volumes
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Author : Armando J L Pombeiro
language : en
Publisher: World Scientific
Release Date : 2024-01-16
Synthesis And Applications In Chemistry And Materials In 4 Volumes written by Armando J L Pombeiro and has been published by World Scientific this book supported file pdf, txt, epub, kindle and other format this book has been release on 2024-01-16 with Science categories.
Chemistry and Material Sciences naturally depend greatly on Synthesis as the initial stage for the existence of compounds and materials with desired behaviors, within the overall streamline of Design/Synthesis — Properties — Application/Function, and their relations. Such a general approach is of a too wide scope to be properly treated in a single set of publications, but this one on 'Synthesis and Applications in Chemistry and Materials' restricts itself by aiming to show the strength and international character of the current research in synthetic chemistry that is being developed in Portugal or abroad by teams that cooperate with this country. Hence, it gathers representative contributions of main Portuguese research groups and foreign collaborating ones. Nevertheless, the topic should be understood in a wide sense, being open to types of studies with significance on sustainable synthesis and applications in chemistry, materials and/or related sciences.
Stereoselective Alkene Synthesis
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Author : Jianbo Wang
language : en
Publisher: Springer
Release Date : 2012-08-13
Stereoselective Alkene Synthesis written by Jianbo Wang and has been published by Springer this book supported file pdf, txt, epub, kindle and other format this book has been release on 2012-08-13 with Science categories.
Stereoselective Synthesis of Tetrasubstituted Alkenes via Torquoselectivity-Controlled Olefination of Carbonyl Compounds with Ynolates, by Mitsuru Shindo and Kenji Matsumoto.- Stereoselective Synthesis of Z-Alkenes, by Woon-Yew Siau, Yao Zhang and Yu Zhao.- Stereoselective Synthesis of Mono-fluoroalkenes, by Shoji Hara.- Recent Advances in Stereoselective Synthesis of 1,3-Dienes, by Michael De Paolis, Isabelle Chataigner and Jacques Maddaluno.- Selective Olefination of Carbonyl Compounds via Metal-Catalyzed Carbene Transfer from Diazo Reagents, by Yang Hu and X. Peter Zhang.- Selective Alkene Metathesis in the Total Synthesis of Complex Natural Product, by Xiaoguang Lei and Houhua Li.- Olefination Reactions of Phosphorus-Stabilized Carbon Nucleophiles, by Yonghong Gu and Shi-Kai Tian.- Alkene Synthesis Through Transition Metal-Catalyzed Cross-Coupling of N-Tosylhydrazones, by Yan Zhang and Jianbo Wang.
Olefin Polymerization
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Author : Walter Kaminsky
language : en
Publisher: Wiley-VCH
Release Date : 2006-08-18
Olefin Polymerization written by Walter Kaminsky and has been published by Wiley-VCH this book supported file pdf, txt, epub, kindle and other format this book has been release on 2006-08-18 with Technology & Engineering categories.
With an enormous velocity, olefin polymerization has expanded to one of the most significant fields in polymers since the first industrial use about 50 years ago. In 2005, 100 million tons of polyolefins were produced - the biggest part was catalyzed by metallorganic compounds. The Hamburg Macromolecular Symposium 2005 with the title "Olefin Polymerization" involved topics such as new catalysts and cocatalysts, kinetics, mechanism and polymer reaction engineering, synthesis of special polymers, and characterization of polyolefins. The conference combined scientists from different disciplines to discuss latest research results of polymers and to offer each other the possibility of cooperation. This is reflected in this volume, which contains invited lectures and selected posters presented at the symposium.
Addition Reactions With Unsaturated Hydrocarbons
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Author : Ruimao Hua
language : en
Publisher: John Wiley & Sons
Release Date : 2022-05-17
Addition Reactions With Unsaturated Hydrocarbons written by Ruimao Hua and has been published by John Wiley & Sons this book supported file pdf, txt, epub, kindle and other format this book has been release on 2022-05-17 with Science categories.
Addition Reactions with Unsaturated Hydrocarbons Provides comprehensive coverage of the atom-economic approach to functionalized molecules using unsaturated hydrocarbons as starting materials Unsaturated hydrocarbons have emerged as an important class of fundamental starting materials in organic synthesis. Synthetic methodologies incorporating unsaturated hydrocarbons continue to expand due to their numerous applications in the synthesis of a vast array of chemicals. Addition Reactions with Unsaturated Hydrocarbons presents an up-to-date overview of modern methods that utilize reactions of unsaturated hydrocarbons as building blocks of organic synthesis, covering the conceptual and practical knowledge required for designing atom-efficient reactions to synthesize functionalized molecules. This authoritative volume discusses homo-dimerization and cross-dimerization of alkynes and/or alkenes, synthesis of carbonyl compounds from the hydration of alkynes, cycloadditions of alkynes and alkenes for the synthesis of carbocycles and heterocycles, double functionalization of alkynes and alkenes by addition reactions of element-element bonds, and more. Summarizes the most recent developments in the reactions of unsaturated hydrocarbons Features more than 600 schemes describing typical reactions starting from unsaturated hydrocarbons Covers topics such as alkynylated reactions, addition and cycloaddition reactions of alkynes and alkenes, and carbonylation of alkynes and alkenes with carbon monoxide Includes examples of synthesis procedures of natural products involving alkyne transformation With comprehensive coverage of important reactions of unsaturated hydrocarbons, Addition Reactions with Unsaturated Hydrocarbons is a valuable resource for organic chemists, pharmaceutical chemists, and biochemists in both academia and industry as well as an excellent reference text for graduate students in relevant areas of chemistry.
Catalytic Asymmetric Synthesis
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Author : Takahiko Akiyama
language : en
Publisher: John Wiley & Sons
Release Date : 2022-05-27
Catalytic Asymmetric Synthesis written by Takahiko Akiyama and has been published by John Wiley & Sons this book supported file pdf, txt, epub, kindle and other format this book has been release on 2022-05-27 with Science categories.
Catalytic Asymmetric Synthesis Seminal text presenting detailed accounts of the most important catalytic asymmetric reactions known today This book covers the preparation of enantiomerically pure or enriched chemical compounds by use of chiral catalyst molecules. While reviewing the most important catalytic methods for asymmetric organic synthesis, this book highlights the most important and recent developments in catalytic asymmetric synthesis. Edited by two well-qualified experts, sample topics covered in the work include: Metal catalysis, organocatalysis, photoredox catalysis, enzyme catalysis C–H bond functionalization reactions Carbon–carbon bond formation reactions, carbon–halogen bond formation reactions, hydrogenations, polymerizations, flow reactions Axially chiral compounds Retaining the best of its predecessors but now thoroughly up to date with the important and recent developments in catalytic asymmetric synthesis, the 4th edition of Catalytic Asymmetric Synthesis serves as an excellent desktop reference and text for researchers and students, from upper-level undergraduates all the way to experienced professionals in industry or academia.