Metal Promoted Selectivity In Organic Synthesis

The demand for selective organic reactions is growing more acute everyday. Indeed, greater product selectivity has an important impact on energy and resource utilization, in terms of reduced process energy requirements for product separation and purification, in terms of low-value by-products, and in terms of environmental acceptance and compatibility. Moreover, more and more chemicals, especially pharmaceuticals, have to be sold in an optically active form. The search for selectivity constitutes a tremendous challenge for the chemists. In the last two decades, homogeneous transition metal based catalysis has emerged as one of the most promising tools for obtaining selectivity. In connection with developments in this area, this book contains updated and expanded versions of most of the lectures presented at a Cornett course held in Trieste (Italy) in 1989 and sponsored by the European Community. A primary aim is to cultivate a deeper understanding of the parameters that govern the selectivities and stimulate a wider utilization of transition metal based catalysis in organic synthesis. All aspects of selectivity, chemo-, regio-, stereo- and enantioselectivity are considered and illustrated by applications in various fields or organic synthesis. The impact of catalysis in oxydation, reduction, carbonylation reactions, carbene chemistry, in Ni and Pd promoted dimerizations, oligomerizations as well as fonctionalisations is stressed, quite often with special emphasis laid on reaction mechanisms. In this aspect, the last chapter examplifies the interest of high pressure NMR and IR when investigating the nature of reaction intermediates in homogeneous reactions.

Carbon Monoxide in Organic Synthesis A thoroughly up-to-date overview of carbonylation reactions in the presence of carbon monoxide In Carbon Monoxide in Organic Synthesis: Carbonylation Chemistry, expert researcher and chemist Bartolo Gabriele delivers a robust summary of the most central advances in the field of carbonylation reactions in the presence of carbon monoxide. Beginning with a brief introduction on the importance of carbon monoxide as a building block in modern organic synthesis, the author goes on to describe metal-catalyzed carbonylations utilizing iron, cobalt, nickel, copper, and manganese. Descriptions of palladium, ruthenium, and rhodium-catalyzed reactions follow, as do discussions of metal-free carbonylation processes. The book is organized by metal to make the book useful as a guide for researchers from both academia and industry whose work touches on the direct synthesis of carbonyl compounds, carboxylic acid derivatives, and heterocycles. It aims to stimulate further discoveries in this rapidly developing field. Readers will also enjoy: A thorough introduction to carbonylations promoted by first row transition metal catalysts, including cobalt-catalyzed and nickel-catalyzed carbonylations An exploration of carbonylations promoted by second row transition metal catalysts, including ruthenium-, rhodium-, palladium(0)-, and palladium (II)-catalyzed carbonylations Practical discussions of miscellaneous carbonylation reactions, including carbonylations promoted by third row transition metal catalysts and metal-free carbonylation processes Perfect for catalytic and organic chemists, Carbon Monoxide in Organic Synthesis: Carbonylation Chemistry is also an indispensable resource for chemists working with organometallics and industrial chemists seeking a summary of important processes used to synthesize value-added products.

Volume 4 focuses on additions and the resulting substitutions at carbon-carbon &pgr;-bonds. Part 1 includes processes generally considered as simple polar reactions, reactive electrophiles and nucleophiles adding to alkenes and alkynes. A major topic is Michael-type addition to electron deficient &pgr;-bonds, featured in the first six chapters. In part 2 are collected the four general processes leading to nucleophilic aromatic substitution, including radical chain processes and transition metal activation through to &pgr;-complexation. Metal-activated addition (generally by nucleophiles) to alkenes and polyenes is presented in part 3, including allylic alkylation catalyzed by palladium. The coverage of nonpolar additions in part 4 includes radical additions, organometal addition (Heck reaction), carbene addition, and 1,3-dipolar cycloadditions.

The continually growing contribution of transition metal chemistry to synthetic organic chemistry is, of course, widely recognized. Equally well known is the difficulty in keeping up-to-date with the multifarious reactions and procedures that seem to be spawned at an ever-increasing rate. These can certainly be summarized on the basis of reviews under the headings of the individual transition metals. More useful to the bench organic chemist, however, would be the opposite type of concordance based on the structural type of the desired synthetic product. This is the approach taken in the present monograph, which presents for each structural entity a conspectus of the transition metal-mediated processes that can be employed in its production. The resulting comparative survey should be a great help in devising the optimum synthetic approach for a particular goal. It is presented from an essentially practical viewpoint, with detailed direc tions interspersed in the Houben-Weyl style. The wide scope of the volume should certainly encourage synthetic organic chemists to utilize fully the range and versatility of these transition metal-mediated processes. This will certainly be a well-thumbed reference book! R. A. RAPHAEL Cambridge University v Preface In recent years an enormous amount of work has been done on the catalysis of organic reactions by various transition metal species and on the organic reactivity of organo-transition-metal compounds.

This first book to comprehensively cover this hot topic presents the information hitherto scattered throughout smaller reviews or single book chapters to provide an introduction to this rapidly expanding field. In ten chapters, the international team of expert authors treats asymmetric syntheses, new transformations, and organometallic reactions using homo- and hetero-bimetallic catalysts. Written for advanced researchers, this very timely publication is of significant benefit to organic and organometallic chemists in both academia and industry.

Activated Metals in Organic Synthesis discusses fundamental principles of the generation of activated, highly reactive metals, and their applications in organic synthesis. Following an introductory chapter on basic forms of metals the chapters in Part 1 are devoted to common strategies utilized for the preparation of active metals. These strategies include vaporization and subsequent co-condensation of metal atoms, in addition to depassivating methods employed commonly in laboratory syntheses. Chapters in Part 2 discuss relevant organic transformations in which metal activation plays a crucial role. Specific topics covered include metal-induced reductive methods; pinacolic, Reformatsky-, and Barbier-type reactions; McMurry ketone-olefin coupling; and the Bernet-Vasella reaction. Each chapter is followed by literature citations ranging from specific references to significant reviews. Many structural formulas are provided, making it easy to follow each synthesis. The book will be an important reference for students, organic chemists, and researchers in all areas of organometallic chemistry.

Based on the papers and posters presented at the 15th Conference on Catalysis of Organic Reactions, this work covers developments in the study of catalysis as it relates to organic synthesis, emphasizing applications in industrial processes. Over 1000 bibliographic citations and over 250 tables, drawings, and photographs are provided. Theoretical and practical aspects of the field are highlighted.

Transition metals open up new opportunities for synthesis, because their means of bonding and their reaction mechanisms differ from those of the elements of the s and p blocks. In the last two decades the subject has mushroomed - established reactions are seeing both technical improvements and increasing numbers of applications, and new reactions are being developed. The practicality of the subject is demonstrated by the large number of publications coming from the process development laboratories of pharmaceutical companies, and its importance is underlined by the fact that three Nobel prizes have been awarded for discoveries in this field in the 21st Century already. Organic Synthesis Using Transition Metals, 2nd Edition considers the ways in which transition metals, as catalysts and reagents, can be used in organic synthesis, both for pharmaceutical compounds and for natural products. It concentrates on the bond-forming reactions that set transition metal chemistry apart from "classical" organic chemistry. Each chapter is extensively referenced and provides a convenient point of entry to the research literature. Topics covered include: introduction to transition metals in organic synthesis coupling reactions C-H activation carbonylative coupling reactions alkene and alkyne insertion reactions electrophilic alkene and alkyne complexes reactions of alkyne complexes carbene complexes h3- or p-allyl -allyl complexes diene, dienyl and arene complexes cycloaddition and cycloisomerisation reactions For this second edition the text has been extensively revised and expanded to reflect the significant improvements and advances in the field since the first edition, as well as the large number of new transition metal-catalysed processes that have come to prominence in the last 10 years – for example the extraordinary progress in coupling reactions using “designer” ligands, catalysis using gold complexes, new opportunities arising from metathesis chemistry, and C-H activation – without neglecting the well established chemistry of metals such as palladium. Organic Synthesis Using Transition Metals, 2nd Edition will find a place on the bookshelves of advanced undergraduates and postgraduates working in organic synthesis, catalysis, medicinal chemistry and drug discovery. It is also useful for practising researchers who want to refresh and enhance their knowledge of the field.