Transition-Metal-Free Enantioselective Reactions of Organo­magnesium Reagents Mediated by Chiral Ligands

Published as part of the Special Section on the Main Group Metal Chemistry Symposium

Abstract

Organomagnesium reagents are among the most important reagents in organic chemistry because of their great utility in forming carbon–carbon bonds. Although most enantioselective reactions using these organometallics involve transmetalation, the past decade has witnessed impressive advances in direct chiral-ligand-mediated reactions of organomagnesiums­. This short review presents an overview of these achievements in enantioselective nucleophilic additions and substitutions.

1 Introduction

2 Enantioselective Nucleophilic Additions

2.1 Addition to C=O Bonds

2.2 Addition to C=N Bonds

2.3 Addition to C=C Bonds

3 Enantioselective Substitution Reactions

3.1 Sulfoxide–Magnesium Exchange

3.2 Desymmetrization via Anhydride Opening

3.3 Asymmetric Allylic Alkylation (AAA)

4 Conclusion

Key words

magnesium - Grignard reaction - asymmetric synthesis - enantioselectivity­ - ligands

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