Copper-Catalyzed Regiodivergent Internal Allylic Alkylations

Abstract

We report a copper-catalyzed, regioselective, and stereospecific alkylation of unbiased internal allylic carbonates with functionalized alkyl and aryl Grignard reagents. The reactions exhibit high stereospecificity and regioselectivity for either SN2 or SN2′ products under two sets of copper-catalyzed conditions, which enables the preparation of a broad range of products with E-alkene selectivity. Density functional theory calculations reveal the origins of the regioselectivity based on the different behaviors of homo- and heterocuprates. © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.