Catalysis in Asymmetric Synthesis

by Caprio, Vittorio; Williams, Jonathan M. J.

• ISBN13: 9781405190916
• ISBN10: 1405190914
• Edition: 2nd
• Format: Hardcover
• Copyright: 2009-03-09
• Publisher: Wiley-Blackwell

Summary

Controlling the stereochemical outcome of reactions in the synthesis of complex natural products or bioactive materials represents a considerable intellectual and practical challenge for chemists. The stereochemical features of these products are usually essential to their bioactivity, so asymmetric synthesis has become a dominant feature of modern organic chemistry. Asymmetric catalysis is an important aspect of asymmetric synthesis, and one that has seen significant progress in the development of widely applicable methodology. This book is written from the point of view of the synthetic organic chemist, illustrating the transformations that can be achieved via this methodology, rather than the organometallic chemistry that lies behind. The emphasis is on non-enzymatic methods of asymmetric catalysis, although key references to enzyme-catalysed reactions have been incorporated where appropriate. The book is extensively referenced and therefore provides a convenient point of entry to the primary literature for both experienced synthetic organic chemists and advanced students alike.

Author Biography

Dr Vittorio Caprio

Lecturer in Organic and Medicinal Chemistry in the Department of Chemistry, University of Auckland, New Zealand. His research interests lie in the application of synthetic organic methods to the synthesis of bioactive natural products of diverse structure. A central aim is the efficient and elegant syntheses of target core structures in a stereocontrolled manner using nature as the source of chirality. The ultimate goal is to use natural medicines as the basis for designing and synthesizing drugs of greater therapeutic value.
 

Professor Jonathan MJ Williams (author of the first edition)

Department of Chemistry, University of Bath, UK

Research involves with the use of transition metals for the synthesis of useful organic molecules.  In particular, we have been developing reactions using ‘borrowing hydrogen.’  In this chemistry, ruthenium or iridium catalysts temporarily remove hydrogen to give an aldehyde.  This aldehyde then reacts to give an alkene (or imine) and the hydrogen is then returned to give a C-C or C-N bond.  These procedures allow alcohols to be used as alkylating agents in place of more conventional, but often toxic/mutagenic alkyl halides.

Table of Contents

Preface to the Second Edition

Preface to the First Edition

Introduction

Reactions Amenable to Asymmetric Catalysis

Assignment of (R) and (S) Stereochemical Descriptors

Futher Reading

References

Reduction of Alkenes

Asymmetric Hydrogenation with Rhodium Complexes

Asymmetric Hydrogenation with Ruthenium Catalysts

Alkene Hydrogenation with Titanium and Zirconium Catalysts

Alkene Hydrogenation with Iridium Catalysts

Alkene Hydrogenation with Organocatalysts

Alkene Hydrosilylation

Alkene Hydroboration

Hydroamination

Hydroformylation

Hydroacylation of Alkenes

Hydrocyanation of Alkenes

References

Reduction of Ketones and Imines

Hydrogenation of Ketones

Hydrogenation and Transfer Hydrogenation of Imines and Related Compounds

Transfer Hydrogenation of Ketones

Heterogeneous Hydrogenation

Reduction of Ketones Using Enantioselective Borohydride Reagents

Hydrosilylation of Ketones

Hydrosilylation of Imines and Nitrones

References

Epoxidation

Epoxidation of Allylic Alcohols

Epoxidation with Metal(salen) Complexes

Epoxidation Using Metal-Porphyrin-Based Catalysts

OtherMetal-Catalysed Epoxidations of Unfunctionalised Olefins

Epoxidation of Electron-Deficient Alkenes

Epoxidation with Iminium Salts

Epoxidation with Ketone Catalysts

Epoxidation of Aldehydes

Aziridination of Alkenes

Aziridination of Imines

References

Further Oxidation Reactions

Dihydroxylation

Aminohydroxylation

+ -Heterofunctionalisation of Aldehydes and Ketones

Oxidation of C-H

Baeyer-Villiger Oxidation

Oxidation of Sulfides

References

Nucleophilic Addition to Carbonyl Compounds

Addition of Organozincs to Carbonyl Compounds

Addition of Cyanide to Aldehydes and Ketones

Allylation of Aldehydes

Hydrophosphonylation of Aldehydes

Nucleophilic Additions to Imines

References

The Aldol and Related Reactions

The Aldol Reaction

Isocyanide and Related Aldol Reactions

The Nitroaldol Reaction

Addition of Enolates to Imines

Darzens Condensation

Morita-Baylis-Hillman Reaction

Carbonyl-Ene Reactions

References

Cycloadditions

Diels-Alder Reactions

Inverse Electron Demand Diels-Alder Reactions

Hetero-Diels-Alder Reactions

1,3-Dipolar Cycloaddition Reactions

[2+2] Cycloadditions

Pauson-Khand-Type Reactions

References

Catalytic Reactions Involving Carbenes and Ylides

Cyclopropanation

Insertion Reactions

Asymmetric Ylide Reactions

References

Catalytic Carbon-Carbon Bond-Forming Reactions

Cross-Coupling Reactions

Metal-Catalysed Allylic Substitution

Heck Reactions

Alkylmetalation of Alkenes.#60

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