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

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.