Herein, we describe the nickel-catalyzed cross-coupling reactions of silyl difluoroenolates with organozinc reagents via C-F bond cleavage (Scheme 1C). The reaction proceeds in a highly regioselective manner to afford stereo-defined silyl fluoroenolates as the kinetic products. Preliminary results for the use of the silyl fluoroenolates for enantioselective asymmetric allylic alkylation reactions are provided. We initiated our study by testing the ability of a Ni(0) complex to cleave a C-F bond in silyl difluoroenolate 1. We chose N-heterocyclic-carbene (NHC) ligands because such systems have already been studied for the cleavage of C(sp 2 )-F bonds. Accordingly, we mixed Ni(cod)2, ICy, and 1 in C6D6, and the reaction was monitored using F NMR spectroscopy. We observed the formation of TMSF, indicating that a C-F bond was cleaved, albeit that the fluoride anion was abstracted by the silicon in 1. Upon examining the literature, we decided to add a lithium salt as a fluoride scavenger to the reaction mixture. Thus, we performed the reaction of 1 with Ni(cod)2/ICy in the presence of LiCl or LiBr, which produced a single peak at around -85 ppm in the F NMR spectra of the crude reaction mixture, which was assigned to the oxidative addition products (E)-2a and (E)-2b (Figure ). The structure of (E)-2a was determined unambiguously using single-crystal X-ray diffraction analysis (Figure ).