The Chemistry of Ynamides


Book Description

Ynamides contain a triple bond directly connected to a nitrogen atom that bears an electron-withdrawing group. They represent an especially useful and emerging class of reagents, notably because of their strongly polarized triple bond, which enables the development of unique chemical transformations. While they were discovered by Viehe in 1972, their chemistry has remained little investigated and the renaissance of ynamide chemistry started at the dawn of the 20th century with the development of efficient methods for their synthesis. Since then, ynamide chemistry has developed at a remarkably high rate, notably in the past 20 years. Although there are several reviews on ynamide chemistry, most of them are out of date or only focus on special aspects of ynamide chemistry and there is no book about ynamide chemistry yet. Thus, a comprehensive book on ynamide chemistry would be timely and is highly needed. This book covers all aspects of ynamide chemistry, including their discovery, their syntheses, their application in heterocyclic chemistry, natural product synthesis, and organometallic chemistry, and their use as coupling reagents. It provides a systematic and comprehensive overview on ynamide chemistry for the researchers in this field, general readers interested in synthesis, and those who want to enter this field and need a comprehensive and up-to-date overview. Undoubtedly, this book will play a key role in connecting the past with the future to further foster the development of ynamide chemistry.




Homologation Reactions


Book Description

Provides a unique summary of homologation strategies in organic synthesis Homologation Reactions presents different concepts underpinning the use of homologating reagents as well as their applications in organic synthesis. It covers in-depth discussions on the rationales governing this kind of transformations with a strong emphasis on mechanistic elements modulating critical aspects (e.g. selectivity) of the processes. In addition, this two-volume work features: Metal carbenoids, ylides, and diazo reagents Homologating agents working under nucleophilic, electrophilic, and radical regime Homologations realized on boron-containing or carbon-centered linchpins Use of highly sensitive fluorinated homologating agents Progressive homologations and the concept of assembly line synthesis Homologation processes followed by rearrangement cascades Construction of cyclic motifs and ring-expansion Homologation reactions with carbon monoxide and carbon dioxide New and/or challenging directions to expect in the future Written by an international team of leaders in the field, the book is a useful guide for designing effective transformations by using homologation reactions. It is a must-read for every synthetic chemist in academia and industry!




Artificial Metalloenzymes and MetalloDNAzymes in Catalysis


Book Description

An important reference for researchers in the field of metal-enzyme hybrid catalysis Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a comprehensive review of the most current strategies, developed over recent decades, for the design, synthesis, and optimization of these hybrid catalysts as well as material about their application. The contributors—noted experts in the field—present information on the preparation, characterization, and optimization of artificial metalloenzymes in a timely and authoritative manner. The authors present a thorough examination of this interesting new platform for catalysis that combines the excellent selective recognition/binding properties of enzymes with transition metal catalysts. The text includes information on the various applications of metal-enzyme hybrid catalysts for novel reactions, offers insights into the latest advances in the field, and contains an informative perspective on the future: Explores the development of artificial metalloenzymes, the modern and strongly evolving research field on the verge of industrial application Contains a comprehensive reference to the research area of metal-enzyme hybrid catalysis that has experienced tremendous growth in recent years Includes contributions from leading researchers in the field Shows how this new catalysis combines the selective recognition/binding properties of enzymes with transition metal catalysts Written for catalytic chemists, bioinorganic chemists, biochemists, and organic chemists, Artificial Metalloenzymes and MetalloDNAzymes in Catalysis offers a unique reference to the fundamentals, concepts, applications, and the most recent developments for more efficient and sustainable synthesis.




Stereoselective Synthesis


Book Description

Carbonyl and imino groups are two of the most integral functional groups employed in organic synthesis. Specific topics discussed: reduction, alkylation, alkenylation, and arylation of these groups, as well as asymmetric aldol, Mannich, and Morita-Bayliss-Hillman reactions. This volume is part of a 3-volume set: Science of Synthesis Stereoselective Synthesis Workbench Edition Further information about Stereoselective Synthesis (including sample pages and the table of contents)




Modern Carbonyl Chemistry


Book Description

The carbonyl group is undoubtedly one of the most important functional groups in organic chemistry, both in its role as reactive center for synthesis or derivatisation and as crucial feature for special structural or physiological properties. Vast and profound progress has been made in all aspects modern carbonyl chemistry. These achievements are, however, rather dispersed in the literature and it is often not easy for the researcher obtain a comprehensive overview of a relevant topic. Modern Carbonyl Chemistry overcomes this inconvenience by collating the information for appropriate themes. In this work internationally renowned experts and leaders in the field have surveyed recent aspects and modern features in carbonyl chemistry, such as cascade-reactions, one-pot-syntheses, recognition, or site differentiation.




Catalytic Asymmetric Synthesis


Book Description

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.




Cooperative Catalysis


Book Description

Written by experts in the field, this is a much-needed overview of the rapidly emerging field of cooperative catalysis. The authors focus on the design and development of novel high-performance catalysts for applications in organic synthesis (particularly asymmetric synthesis), covering a broad range of topics, from the latest progress in Lewis acid / Br?nsted base catalysis to e.g. metal-assisted organo catalysis, cooperative metal/enzyme catalysis, and cooperative catalysis in polymerization reactions and on solid surfaces. The chapters are classified according to the type of cooperating activating groups, and describe in detail the different strategies of cooperative activation, highlighting their respective advantages and pitfalls. As a result, readers will learn about the different concepts of cooperative catalysis, their corresponding modes of operation and their applications, thus helping to find a solution to a specific synthetic catalysis problem.




C-C Bond Activation


Book Description

The series Topics in Current Chemistry presents critical reviews of the present and future trends in modern chemical research. The scope of coverage is all areas of chemical science including the interfaces with related disciplines such as biology, medicine and materials science. The goal of each thematic volume is to give the non-specialist reader, whether in academia or industry, a comprehensive insight into an area where new research is emerging which is of interest to a larger scientific audience. Each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years are presented using selected examples to illustrate the principles discussed. The coverage is not intended to be an exhaustive summary of the field or include large quantities of data, but should rather be conceptual, concentrating on the methodological thinking that will allow the non-specialist reader to understand the information presented. Contributions also offer an outlook on potential future developments in the field. Review articles for the individual volumes are invited by the volume editors. Readership: research chemists at universities or in industry, graduate students




Strategies and Tactics in Organic Synthesis


Book Description

Strategies and Tactics in Organic Synthesis, Volume 13, provides a forum for investigators to discuss their approach to the science and art of organic synthesis. Rather than a simple presentation of data or a secondhand analysis, this classic provides stories that vividly demonstrate the power of the human endeavor known as organic synthesis and the creativity and tenacity of its practitioners. Firsthand accounts of each project present the excitement of conception, the frustration of failure and the joy experienced when either rational thought or good fortune gives rise to the successful completion of a project. Readers will be educated, challenged and inspired by these accounts, which portray the idea that triumphs do not come without challenges. This innovative approach also helps illustrate how challenges to further advance the science and art of organic synthesis can be overcome, driving the field forward to meet the demands of society by discovering new reactions, creating new designs and building molecules with atom and step economies that provide functional solutions to create a better world. - Presents state-of-the-art developments in organic synthesis - Provides insight and offers new perspective to problem-solving - Written by leading experts in the field - Uses firsthand narrative accounts to vividly illustrate the challenges and joys involved in advancing the science of organic synthesis




The Chemoselective Catalytic Oxidation of Alcohols, Diols, and Polyols to Ketones and Hydroxyketones


Book Description

The chemoselective oxidation of vicinal diols to α-hydroxyketones is a challenge in organic syntheses because not only does the diol need to be oxidized selectively to a monocarbonyl compound, but diols are also prone to overoxidation and oxidative cleavage. Employing a cationic palladium complex, [(neocuproine)Pd(OAc)]2(OTf)2, we were able to demonstrate the selective oxidation of glycerol to dihydroxyacetone mediated by either benzoquinone or O2 as the terminal oxidant, an accomplishment that has little precedent in homogeneous catalysis. Mechanistic studies were undertaken to uncover the nature of this remarkable chemoselectivity. Kinetic and deuterium-labeling studies implicate reversible β-hydride elimination from isomeric Pd alkoxides and turnover-limiting displacement of the dihydroxyacetone product by benzoquinone. We successfully extended this methodology to other terminal 1,2-diols and symmetric vicinal 1,2-diols and have carried out aerobic oxidation of these substrates catalyzed by 1. Examination of the reactivity of 1 with conformationally-restricted 1,2-cyclohexanediols suggests that the diol must chelate to the Pd center for effective oxidation to the hydroxyketone product. In a separate project, we have also investigated the electrocatalytic reduction of dioxygen by several dinuclear copper complexes, an important reaction for fuel cell applications.