Synthesis 2018; 50(18): 3589-3602
DOI: 10.1055/s-0037-1610135
short review
© Georg Thieme Verlag Stuttgart · New York

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

Hélène Guyon
IMMM – UMR 6283 CNRS, Le Mans Université, avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France   Email: Anne.Boussonniere@univ-lemans.fr   Email: Anne-Sophie.Castanet@univ-lemans.fr
,
IMMM – UMR 6283 CNRS, Le Mans Université, avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France   Email: Anne.Boussonniere@univ-lemans.fr   Email: Anne-Sophie.Castanet@univ-lemans.fr
,
IMMM – UMR 6283 CNRS, Le Mans Université, avenue Olivier Messiaen, 72085 Le Mans Cedex 9, France   Email: Anne.Boussonniere@univ-lemans.fr   Email: Anne-Sophie.Castanet@univ-lemans.fr
› Author Affiliations
This work was supported by the French Ministry of Higher Education, Research and Innovation (H. G. Ph.D. fellowship), the CNRS and Le Mans Université.
Further Information

Publication History

Received: 28 February 2018

Accepted after revision: 11 April 2018

Publication Date:
20 June 2018 (online)


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

 
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