Nickel-Catalyzed Stereoselective Cascade C–F Functionalizations of gem-Difluoroalkenes

The activation and functionalization of C–F bonds for the construction of C–C and C–X bonds have drawn significant research attention in recent years. However, the chemo- and stereoselective control of dual C–F bond functionalization of gem-difluoroalkenes remains a formidable challenge. Herein, a Ni-catalyzed reductive cross-coupling of gem-difluoroalkenes with alkenyl-electrophiles and D2O that allowed the generation of C(sp2)–C(sp2) bonds and C(sp2)–D bonds in one pot by successive defluorination is described. This methodology offers facile access to various deuterated 1,3-dienes with broad functional group compatibility and (E)-selectivity under mild conditions. Preliminary mechanistic studies indicate that α-alkenyl-substituted monofluoroalkenes might be intermediates in this protocol.