Branch-Selective Alkene Hydroarylation by Cooperative Destabilization: Iridium-Catalyzed ortho-Alkylation of Acetanilides

An iridium(I) catalyst system, modified with the wide‐bite‐angle and electron‐deficient bisphosphine dFppb (1,4‐bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch‐selective hydroarylation reactions between diverse acetanilides and aryl‐ or alkyl‐substituted alkenes. This provides direct and ortho‐selective access to synthetically challenging anilines, and addresses long‐standing issues associated with related Friedel–Crafts alkylations. An iridium(I) catalyst system modified with the wide‐bite‐angle and electron‐deficient bisphosphine dFppb (1,4‐bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch‐selective hydroarylation reactions between diverse acetanilides and aryl‐ or alkyl‐substituted alkenes. This provides direct and ortho‐selective access to synthetically challenging anilines.