Atroposelective Dearomative Cross‐Coupling of Benzofuran Derivatives by Z‐Selective Functionalization of the Vinyl C─O Bond

Abstract

ABSTRACT Catalytic asymmetric transformation of benzofuran derivatives has received significant attention owing to its capacity to prepare chiral molecules from readily available feedstocks. Herein, an unprecedented asymmetric cross‐coupling of benzofuran derivatives is reported for the construction of axial chirality. Employing a chiral nickel catalyst, this approach is achieved through direct enantio‐ and Z‐selective dearomative functionalization of the vinyl C─O bond, providing efficient access to valuable atropisomeric acyclic alkenes. A broad substrate scope is demonstrated under mild conditions. Moreover, experimental and theoretical mechanistic studies suggest that the stereochemical outcome is facilitated by a dynamic epimerization between diastereomeric six‐membered ( Z )‐styryl‐nickelacycle intermediates.