Dual-Catalysis-Enabled Construction of Vicinal Stereogenic Centers through Diastereo- and Enantioselective Allylic Substitution

Abstract

Vicinal stereogenic centers represent prevalent structural motifs in organic synthetic chemistry, and their construction poses a longstanding challenge. Transition-metal-catalyzed asymmetric allylic substitution has become a well-established enantioselective C–C bond-forming reaction. When these reactions involve a prochiral nucleophile and an allylic electrophile with a terminal substituent, the creation of vicinal stereogenic centers becomes feasible. However, despite remarkable achievements having been accomplished, realizing this transformation with precise control over both the enantio- and diastereoselectivity remains a significant challenge. To address the stereoselective challenges, the introduction of a second catalyst to the transition-metal-catalyzed asymmetric allylic alkylation to control the diastereoselectivity during C–C bond formation has proven particularly fruitful. In this short review, we aim to highlight recent advances in dual catalysis that enable diastereo- and enantioselective allylic substitutions.

1 Introduction

2 Construction of Vicinal Stereogenic Centers by Organo and Metal Dual Catalysis

2.1 Chiral Phase-Transfer Catalysis and Transition-Metal Dual Catalysis

2.2 Chiral Amine and Transition-Metal Dual Catalysis

2.3 NHC and Transition-Metal Dual Catalysis

2.4 Chiral Aldehyde and Transition-Metal Dual Catalysis

2.5 Chiral Lewis Base and Transition-Metal Dual Catalysis

3 Construction of Vicinal Stereogenic Centers by Metal and Metal Dual Catalysis

3.1 Lewis Acidic Metal and Iridium Dual Catalysis

3.2 Lewis Acidic Metal and Palladium Dual Catalysis

3.3 Palladium and Ruthenium Dual Catalysis

3.4 Other Advancements in the Construction of Vicinal Stereogenic Centers through Synergistic Bimetallic Catalysis Enabling Asymmetric Allylic Alkylation

4 Conclusions and Future Outlook

Key words

transition-metal-catalyzed allylic alkylation - asymmetric allylic substitution - vicinal stereogenic centers - dual catalysis - synergistic catalysis

Publication History

Received: 05 March 2024

Accepted after revision: 02 April 2024

Article published online:
15 April 2024

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