1,1-Diborylalkanes as Versatile Precursors for Copper-Catalyzed Diastereo- and Enantioselective Allylic Substitution

Abstract

While copper-catalyzed asymmetric allylic alkylation has undergone substantial advances, achieving high levels of stereocontrol with hard nucleophiles remains a formidable challenge. We have recently reported an efficient copper-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of allyl bromides using 1,1-diborylalkanes as prochiral hard nucleophiles. This methodology employs CuBr as a catalyst, an (R)-BINOL-derived phosphoramidite as a chiral ligand, and lithium benzoate as a crucial additive, providing enantioenriched homoallylic boronic esters in good yields with excellent stereoselectivity. Our mechanistic investigations revealed that lithium benzoate is the key to facilitating highly selective anti-S_N2′-type oxidative addition, offering valuable insights for further development of asymmetric copper catalysis.

1 Introduction

2 Copper-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation with 1,1-Diborylalkanes

3 Conclusions and Perspectives

Key words

copper - allylic substitution - chiral organocopper - diastereoselectivity - enantioselectivity

Publication History

Received: 12 March 2025

Accepted after revision: 16 April 2025

Accepted Manuscript online:
16 April 2025

Article published online:
13 June 2025

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