Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions with Nitrile-Stabilized Carbanions

Mai-Jan Tom; P. Andrew Evans

doi:10.1055/a-1696-5713

Synlett, Table of Contents

Synlett 2022; 33(10): 939-951
DOI: 10.1055/a-1696-5713

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Asymmetric Rhodium-Catalyzed Allylic Substitution Reactions with Nitrile-Stabilized Carbanions

Mai-Jan Tom

^aDepartment of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada

,

P. Andrew Evans∗

^aDepartment of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario, K7L 3N6, Canada

^bXiangya School of Pharmaceutical Sciences, Central South University, Changsha 410013, Hunan, P. R. of China

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Abstract

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Abstract

This Account summarizes our recent work on rhodium-catalyzed allylic alkylation reactions with nitrile-stabilized carbanions. Despite the challenges associated with employing nitrile-stabilized nucleophiles in transition-metal-catalyzed reactions, we have developed enantiospecific and enantioselective allylic alkylation reactions. Notably, these novel reactions permit expedient and selective access to an array of acyclic ternary and quaternary stereogenic centers present in important biologically active and functional molecules.

1 Introduction

2 Enantiospecific Allylic Alkylation Reactions with Nitrile-Stabilized Anions

3 Enantioselective Allylic Alkylation Reactions with Nitrile-Stabilized Anions

4 Conclusion

Key words

allylic alkylation - enantioselective - enantiospecific - nitrile anion - regioselective - total synthesis

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