We also tested other gem-difluoroalkenes to explore the potential versatility of our defluorinative coupling. When we performed the reaction using 1-(2,2difluorovinyl)naphthalene (7a), we observed the formation of (Z)-8a, which is a typical product based on other, hitherto reported defluorinative coupling reactions of gemdifluoroalkenes (Figure , left). In our case, the major product was 1-(2,2diphenylvinyl)naphthalene (49%). In contrast, the reaction of 7b having a methyl group furnished (E)-8b in excellent yield (Figure , right). This result represents a rare example of highly stereoselective C-F bond coupling with a disubstituted gemdifluoroalkene without a directing group. The preliminary results of the asymmetric Tsuji-Trost reaction 67,68 using our acyclic silyl fluoroenolates are summarized in Table . We first tested the reaction of (Z)-6a and allyl ethyl carbonate in the presence of catalytic amounts of [Pd(C3H5)Cl]2 and (S)-tBu-PHOX (entry 1). We added tetrabutylammonium triphenyldifluorosilicate (TBAT) to activate the silyl group according to Paquin's report. Disappointingly, the desired product (9) was racemic. When we omitted the addition of TBAT to prevent the rapid E/Z isomerization of 6a (Scheme S2), 9 was obtained in 11% ee, although the yield was only 15% (entry 2). Gratifyingly, the reaction of (Z)-6m, which did not isomerize in the presence of TBAT, furnished ketone 10 in 33% yield and 79% ee (entry 3). When we attempted a reaction using a stoichiometric amount of TBAT, we obtained 10 in 73% yield with 68% ee (entry 4). The benzyl group is important for good enantioselectivity, since the related reactions using a ketoester or allyl carbonate have been reported to furnish 11 in 51% ee and 36% ee , respectively.