Regioselective C−F Bond Transformations of Silyl Difluoroenolates

Herein, we report the development of a nickel-catalyzed cross-coupling reaction of silyl difluoroenolates with aryl zinc reagents via C−F bond cleavage. Treatment of a stoichiometric amount of Ni(0)/ N-heterocyclic carbene (NHC) with silyl difluoroenolates in the presence of a lithium salt resulted in C−F bond cleavage to selectively afford the corresponding (Z)-alkenyl Ni complexes. Density functional theory (DFT) calculations revealed the importance of the silyl substituent in creating environments with varying steric hindrance for each of the two fluorine atoms. Based on these observations, we developed a catalytic cross-coupling reaction that selectively delivers a single geometric isomer of a fluoroenolate.