Nickel-Catalyzed Cross-Electrophile Coupling Reactions between Allylic Acetates and gem -Difluorovinyl Tosylate.

A nickel-catalyzed cross-electrophile coupling of allylic acetates and gem -difluorovinyl tosylate is presented, which first achieves allylic gem -difluoroolefins via C(sp 3 )-C(sp 2 ) cross-electrophile coupling. In addition, this protocol was performed under mild reaction conditions, affording a variety of allylic gem -difluorovinyl arenes in moderate to good yields. Moreover, both linear and branched allylic acetate could produce a linear cross-coupling product exclusively. Mechanistic studies reveal that the reaction involves two different Ni(0)/Ni(II) catalytic cycles.