Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Over the past 20 years, the asymmetric synthesis of acyclic tetrasubstituted stereocenters by Pd-catalyzed asymmetric allylic alkylation (Pd-AAA) strategies has seen considerable growth. Despite the inherent difficulty in accessing acyclic tetrasubstituted stereocenters, creative approaches toward this problem have resulted in high stereoinduction on both electrophilic and nucleophilic reaction partners. Much of this chemistry has paved the way for unique solutions in Mo-, Ir-, and Rh-AAA, with many complimentary methods arising due to the unique regiochemical outcomes of AAA outside of Pd catalysis.

1 Introduction

2 Stereocontrol on Prochiral Electrophiles

3 Stereocontrol on Prochiral Nucleophiles

4 Temporary Cyclic Pronucleophiles

5 Allylic Alkylation with Other Metals

6 Conclusions and Outlook

Key words

allylic alkylation - acyclic stereocontrol - tertiary alcohols - α-tertiary amines - quaternary carbon stereocenters

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