Nickel-Catalyzed Stereo- and Enantioselective Cross-Coupling of gem-Difluoroalkenes with Carbon Electrophiles by C-F Bond Activation

Stereo- and enantioselective cross-electrophile coupling involving C-F bond activation is reported. Treatment of gem-difluoroalkenes with racemic benzyl electrophiles in the presence of a chiral nickel complex using B(2)pin(2) as a stoichiometric reductant allows the construction of a C(sp(2))-C(sp(3)) bond under mild conditions, affording a broad range of monofluoroalkenes bearing stereogenic allylic centers. Initial mechanistic studies indicate that a radical chain pathway may be operating, wherein the ester group in the gem-difluoroalkene promotes C-F bond activation through oxidative addition to a Ni species.