NiH‐Catalyzed Migratory Defluorinative Olefin Cross‐Coupling: Trifluoromethyl‐Substituted Alkenes as Acceptor Olefins to Form gem‐Difluoroalkenes

Abstract We report a NiH‐catalyzed migratory defluorinative coupling between two electronically differentiated olefins. A broad range of unactivated donor olefins can be joined directly to acceptor olefins containing an electron‐deficient trifluoromethyl substituent in both intra‐ and intermolecular fashion to form gem ‐difluoroalkenes. This migratory coupling shows both site‐ and chemoselectivity under mild conditions, with the formation of a tertiary or quaternary carbon center.