Transition-Metal-Catalyzed Allylic Substitution Reactions: Stereoselective Construction of α- and β-Substituted Carbonyl Compounds

Samuel Oliver; P. Andrew Evans

doi:10.1055/s-0033-1338538

Synthesis, Table of Contents

Synthesis 2013; 45(23): 3179-3198
DOI: 10.1055/s-0033-1338538

review

Transition-Metal-Catalyzed Allylic Substitution Reactions: Stereoselective Construction of α- and β-Substituted Carbonyl Compounds

Samuel Oliver

^aDepartment of Chemistry, The University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK

,

P. Andrew Evans*

^bDepartment of Chemistry, Queen’s University, 90 Bader Lane, Kingston, ON, K7L 3N6, Canada Fax: +1(610)5336669 Email: Andrew.Evans@chem.queensu.ca

› Author Affiliations

Abstract

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Dedicated to Professor Andrew B. Holmes on the occasion of his 70^th birthday

Abstract

The stereoselective synthesis of α- and β-substituted carbonyl compounds remains a significant area of interest in organic chemistry. This is largely due to their ubiquity and versatility as synthetic intermediates and the importance of this functionality in a range of biologically important agents. In this context, the transition-metal-catalyzed allylic substitution provides an extremely powerful tool for the asymmetric construction of a variety of α- and β-tertiary and quaternary substituted carbonyl compounds. This review highlights pertinent historical developments of these reactions, from the seminal work with enolate equivalents to the more recent developments with unstabilized enolates and acyl anions. It also outlines the most important mechanistic aspects of these transformations in order to provide insight into the current scope and limitations and potential areas for further development.

1 Introduction

2 Unstabilized Enolate Nucleophiles

2.1 Enolate Equivalents

2.1.1 Enamines

2.1.2 Imines

2.1.3 Silyl Enol Ethers

2.1.4 Enolstannanes

2.1.5 Decarboxylative Approaches

2.2 Metal Enolates

2.2.1 Boron Enolates

2.2.2 Tin Enolates

2.2.3 Copper Enolates

2.2.4 Zinc Enolates

2.2.5 Magnesium Enolates

2.2.6 Sodium Enolates

2.2.7 Lithium Enolates

3 Acyl Anion Equivalents

3.1 Acylmetal Nucleophiles

3.2 ‘Masked’ Acyl Anion Equivalents

4 Conclusions

Key words

acyl anion - allylic substitution - asymmetric catalysis - enamine - enolate - metal-catalyzed - silyl enol ethers

Full Text

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