Synthetic and Mechanistic Studies on the Cross-Coupling Reactions Catalyzed by Ruthenium Complexes

Synthetic and Mechanistic Studies on the Cross-Coupling Reactions Catalyzed by Ruthenium Complexes
Author: Ruili Gao
Publisher:
Total Pages:
Release: 2011
Genre: Chemical bonds
ISBN:

Download Synthetic and Mechanistic Studies on the Cross-Coupling Reactions Catalyzed by Ruthenium Complexes Book in PDF, Epub and Kindle

Transition metal catalyzed C-H bond activation reaction is a powerful synthetic method for forming functionalized products directly from unreactive hydrocarbons, and has enormous synthetic potentials for developing chemical processes ranging from petroleum products to pharmaceutical agents. In an attempt to mimic the high stereo selectivity and region selectivity of catalytic reactions by transition metal catalysts, recent research has focused on design and synthesis of transition metal complex and the application on the coupling reactions involving C-H bond activation. Herein, we wish to report the highly effective coupling reactions involving C-H bond activation by using well-defined ruthenium catalysts. Ruthenium hydride complex was to found to have high activity and selectivity for hydrosilylation, silyl enol ethers formation and enol esters formation reactions. Throughout the course of the mechanistic investigation of the reactions, we found compelling evidence for mechanism of reactions by spectroscopic, structural techniques and computational (DFT) analysis.

Synthetic and Mechanistic Investigations of Ruthenium Alkylidene-catalyzed Alkene-silane Cross-coupling Reactions

Synthetic and Mechanistic Investigations of Ruthenium Alkylidene-catalyzed Alkene-silane Cross-coupling Reactions
Author: Apparao Bokka
Publisher:
Total Pages: 287
Release: 2017
Genre: Organometallic chemistry
ISBN:

Download Synthetic and Mechanistic Investigations of Ruthenium Alkylidene-catalyzed Alkene-silane Cross-coupling Reactions Book in PDF, Epub and Kindle

Grubbs-type ruthenium alkylidene-catalyzed intramolecular alkene hydrosilylation and intermolecular dehydrogenative silylation and hydrosilylation of vinylarenes have been achieved with high regio- and stereoselectivity. Mechanistic details to support the initial activation of ruthenium complex have been revealed. Chapter 1 describes the uses of organosilanes in various fields. Development of transition metal-catalyzed hydrosilylations, alkene/alkyne metathesis activities of Grubbs-type ruthenium alkylidenes and non-metathetical activities including hydrosilylation of alkynes are discussed. The development of intramolecular hydrosilylation of alkenylsilyl ethers through reaction discovery and optimization is discussed. The strategy developed has been tested successfully on a variety of substrates with varying steric and electronic properties. A plausible mechanism is proposed for the activation of the ruthenium complex by direct [sigma]-bond metathesis between Si-H and Ru-Cl. Specifically a mechanistic pathway for intramolecular alkene hydrosilylation catalyzed by ruthenium alkylidene complexes was proposed based on experimental observations from the optimization studies, isotope labelling studies, the investigation of base and halide effects. In Chapter 2, the synthesis and uses of vinyl and alkyl silanes and existing methods to synthesize vinylsilanes have been discussed. The discovery and development of dehydrogenative silylation and hydrosilylation of vinylarenes using Grubbs-type ruthenium alkylidene complexes are presented. Reaction optimization to selectively achieve the formation of vinyl and alkyl silanes by varying the L and X-type ligands has been demonstrated. Evaluation of sacrificial hydrogen acceptors (SHA) and the investigation on substrate scope for the dehydrogenative and hydrosilylation were explored. This chapter also rationalizes possible mechanistic pathways for dehydrogenative and hydrosilylation catalyzed by ruthenium alkylidene complexes varying L and X-type ligands. Mechanistic studies on isotope labelling experiments and ligand effect revealing the rate-determining step for both the transformations are discussed.

Ruthenium in Organic Synthesis

Ruthenium in Organic Synthesis
Author: Shun-Ichi Murahashi
Publisher: John Wiley & Sons
Total Pages: 398
Release: 2006-03-06
Genre: Science
ISBN: 3527605797

Download Ruthenium in Organic Synthesis Book in PDF, Epub and Kindle

In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry. From the contents: Introduction (S.-I. Murahashi) Hydrogenation and Transfer Hydrogenation (M. Kitamura and R. Noyori) Oxidations (S.-I. Murahashi and N. Komiya) Carbon-Carbon Bond Formations via Ruthenacycle Intermediates (K. Itoh) Carbon-Carbon Bond Formation via pi-Allylruthenium Intermediates (T. Mitsudo) Olefin Metathesis (R. H. Grubbs) Cyclopropanation (H. Nishiyama) Nucleophilic Addition to Alkynes and Reactions via Vinylidene Intermediates (P. Dixneuf) Reactions via C-H Activation (N. Chatani) Lewis Acid Reactions (E. P. Kundig) Reactions with CO and CO2 (T. Mitsudo) Isomerization of Organic Substrates Catalyzed by Ruthenium Complexes (H. Suzuki) Radical Reactions (H. Nagashima) Bond Cleavage Reactions (S. Komiya)

Oxidative Cross-Coupling Reactions

Oxidative Cross-Coupling Reactions
Author: Aiwen Lei
Publisher: John Wiley & Sons
Total Pages: 243
Release: 2016-11-14
Genre: Technology & Engineering
ISBN: 3527336885

Download Oxidative Cross-Coupling Reactions Book in PDF, Epub and Kindle

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.

Nickel- and Palladium-Catalyzed Cross Coupling Reactions

Nickel- and Palladium-Catalyzed Cross Coupling Reactions
Author: Rebecca Green
Publisher:
Total Pages: 183
Release: 2016
Genre:
ISBN:

Download Nickel- and Palladium-Catalyzed Cross Coupling Reactions Book in PDF, Epub and Kindle

The following dissertation discusses the development of a nickel catalyst for the synthesis of Csp2-Csp bonds in addition to the development and mechanistic studies of nickel and palladium catalysts for the synthesis of Csp2-N bonds. The first chapter is a review of the cross-coupling reactions discussed in this dissertation. Nickel and palladium will be compared with respect to physical properties and reactivity differences. The challenges associated with nickel-catalyzed cross coupling will be illustrated, while drawing analogies to analogous palladium-catalyzed reactions. The literature background for the synthesis of Csp2-Csp bonds, catalyzed by palladium and palladium/copper catalytic systems, will be reviewed, while highlighting the challenges and limitations of the field. The field of Csp2-N bond-forming reactions will be examined, as the differences in reactivity between nickel and palladium will be emphasized. Chapter 2 discusses our efforts towards the development of a nickel catalyst for the development of a Csp2-Csp bond forming reaction, performed in the absence of a copper co-catalyst. Chapter 3 describes the development of a single-component nickel complex that catalyzes the coupling of aryl chlorides with primary alkylamines. A series of mechanistic experiments, including synthesis of catalytic intermediates and kinetic experiments, were performed to elucidate the mechanism of the reaction. Chapter 4 discusses our report the palladium-catalyzed coupling of aryl halides withammonia and gaseous amines as their ammonium salts. A difference in selectivity between reactions of aryl chlorides and aryl bromides was discovered and investigated. Chapter 5 describes the development of a single-component nickel catalyst for the coupling of aryl chlorides with ammonia and ammonium sulfate to form the corresponding primary arylamines. The application of ammonium salts was extended to the coupling of gaseous amines, such as methylamine and ethylamine, which were subjected to the reaction conditions as their hydrochloride salt.

Metal Catalyzed Cross-Coupling Reactions and More

Metal Catalyzed Cross-Coupling Reactions and More
Author: Armin de Meijere
Publisher: John Wiley & Sons
Total Pages: 1640
Release: 2013-12-04
Genre: Science
ISBN: 3527655603

Download Metal Catalyzed Cross-Coupling Reactions and More Book in PDF, Epub and Kindle

This three volume book is the follow-up handbook to the bestselling volume "Metal-Catalyzed Cross-Coupling Reactions", the definitive reference in the field. In line with the enormous developments in this area, this is not a new edition, but rather a new book in three volumes with over 50% more content. This new content includes C-H activation, shifting the focus away from typical cross-coupling reactions, while those topics and chapters found in de Meijere/Diederich's book have been updated and expanded. With its highly experienced editor team and the list of authors reading like an international Who's-Who in the field, this work will be of great interest to every synthetic chemist working in academia and industry.

Cross-Coupling Reactions

Cross-Coupling Reactions
Author: Norio Miyaura
Publisher: Springer
Total Pages: 253
Release: 2003-07-01
Genre: Science
ISBN: 354045313X

Download Cross-Coupling Reactions Book in PDF, Epub and Kindle

In 1972, a very powerful catalytic cycle for carbon-carbon bond formation was 2 first discovered by the coupling reaction of Grignard reagents at the sp -carbon. Over the past 30 years, the protocol has been substantially improved and expanded to other coupling reactions of Li,B,N,O,Al,Si,P,S,Cu,Mn,Zn,In,Sn, and Hg compounds. These reactions provided an indispensable and simple methodology for preparative organic chemists. Due to the simplicity and rel- bility in the carbon-carbon, carbon-heteroatom, and carbon-metalloid bo- formations,as well as high efficiency of the catalytic process,the reactions have been widely employed by organic chemists in various fields. Application of the protocol ranges from various syntheses of complex natural products to the preparation of biologically relevant molecules including drugs, and of sup- molecules, and to functional materials. The reactions on solid surfaces allow robot synthesis and combinatorial synthesis. Now, many organic chemists do not hesitate to use transition metal complexes for the transformation of org- ic molecules. Indeed, innumerable organic syntheses have been realized by the catalyzed reactions of transition metal complexes that are not achievable by t- ditional synthetic methods. Among these, the metal-catalyzed cross-coupling reactions have undoubtedly contributed greatly to the development of such a new area of “metal-catalyzed organic syntheses”. An excellent monograph for the cross-coupling reactions and other met- catalyzed C-C bond-forming reactions recently appeared in Metal-catalyzed Cross-coupling Reactions (Wiley-VCH,1998).

Advances in Cross-Coupling Reactions

Advances in Cross-Coupling Reactions
Author: José Pérez Sestelo
Publisher: MDPI
Total Pages: 234
Release: 2020-12-03
Genre: Science
ISBN: 3039435671

Download Advances in Cross-Coupling Reactions Book in PDF, Epub and Kindle

In this Special Issue, recent advances in cross-coupling reactions are presented in the form of original research articles, reviews, and short communications. These contributions cover different topics in this area, including novel coupling reactions, reaction conditions, synthetic alternatives, metal ligands, and applications for new pharmaceutical compounds and organic materials. In particular, the reviews deal with methodologies such as the synthesis of diarylketones through palladium catalysis and the most relevant examples of Suzuki–Miyaura and Buchwald–Hartwig coupling reactions in the synthesis of bioactive compounds. The synthetic utility of cross-coupling reactions for the synthesis of medium-size rings and the utility of Stille and Suzuki coupling reactions for the synthesis of new molecular machines based on sterically hindered anthracenyl trypticenyl units are also summarized. The original research articles present the synthesis of 2-alkynylpyrrols by inverse Sonogashira coupling and the synthesis of indoles under oxidative dearomative cross-dehydrogenative conditions. The efficient combination of iridium-catalyzed C–H borylation of aryl halides with the Sonogashira coupling and a sequential iridium-catalyzed borylation of NH-free pyrroles followed by a Suzuki–Miyaura reaction are included. The synthesis of aryl propionic acids, a common structural motif in medicinal chemistry, and the synthesis of new organic dyes are also covered.

Metal-catalyzed Cross-coupling Reactions

Metal-catalyzed Cross-coupling Reactions
Author: François Diederich
Publisher: Wiley-VCH
Total Pages: 552
Release: 1998-02-11
Genre: Science
ISBN:

Download Metal-catalyzed Cross-coupling Reactions Book in PDF, Epub and Kindle

Carbon-carbon bond forming reactions are arguably the most important processes in chemistry, as they represent key steps in the building of complex molecules from simple precursors. Among these reactions, metal-catalyzed cross-coupling reactions are extensively employed in a wide range of areas of preparative organic chemistry, ranging from the synthesis of complex natural products, to supramolecular chemistry, and materials science. In this work, a dozen internationally renowned experts and leaders in the field bring the reader up to date by documenting and critically analyzing current developments and uses of metal-catalyzed cross-coupling reactions. A particularly attractive and useful feature, that enhances the practical value of this monograph, is the inclusion of key synthetic protocols, in experimental format, chosen for broad utility and application. This practice-oriented book can offer the practitioner short cuts to ensure they remain up-to-date with the latest developments.