Desulfonylation-Initiated Distal Alkenyl Migration in Copper-Catalyzed Alkenylation of Unactivated Alkenes.

A novel and efficient protocol for desulfonylation-initiated distal alkenyl migration and its application to the elusive alkenylation of unactivated alkenes have been presented. This radical cascade process has successfully achieved the vicinal difluoroalkylalkenylation of unactivated alkenes with excellent chemo-, regio-, and stereoselectivity in high efficiency under mild conditions. The reactions afford previously unknown 3,3-difluoro-5-styrylpiperidin-2-one derivatives or β-styryl-γ-difluoroalkyl amines bearing a quaternary stereocenter. This is the first report of difunctionalization of unactivated alkenes through desulfonylation-initiated distal alkenyl migration.