The results of the stoichiometric reactions encouraged us to develop a catalytic reaction using aryl zinc reagents. For that purpose, we prepared diphenylzinc via the transmetallation of the corresponding Grignard reagent with ZnBr2. Then, 1 was treated with diphenylzinc in the presence of 10 mol% Ni(cod)2, 20 mol% ICy, and 2 equivalents of LiBr in THF at 60 °C. Unfortunately, the reaction quantitatively furnished the disubstituted product 4 instead of the desired fluoroenolate (3) (Table , entry 1). The formation of 4 indicates that the cleavage of the second C-F bond in 3 is favored over the dissociation of 3 from the nickel center. Thus, we tested the bulkier IAd ligand (entry 2), which forced the removal of 3 due to steric hindrance. The yield of 3 was slightly improved to 3%, although 4 was still a major product (entry 2). When we switched to the N-aryl-type ligand IMes, the yield of 3 increased to 13% (entry 3), and the use of the more sterically hindered IPr and SIPr furnished 3 in 44% and 39% yield (major product), respectively (entries 4 and 5). A comparison of the structures and reaction yields of IMes and IPr suggested that the introduction of bulkier substituents at the benzylic positions of the aniline moieties could be beneficial. Ultimately, we used IPr* 51 to obtain 3 in 82% yield (entry 6). Control experiments revealed that the addition of both Ni and IPr* is crucial to obtain 3 in high yield, albeit the addition of Ni(cod)2 alone gave the coupling product in poor yield (entries 7-9). We next investigated the effect of salts on the yield of the cross-coupling reaction. When we ran the reaction without lithium salt, we obtained the desired product in moderate yield (entry 10). In contrast, the reaction using isolated ZnPh2 (under Li-and Mg-free conditions) delivered the desired product in low yield (entry 11). In this case, ~15% TMSF was observed in the F NMR spectrum of the crude reaction mixture. Taken together, these results indicate that Mg salts could also promote the reaction in a way similar to that of Li salts, while the silyl enolate itself can also act as a fluoride scavenger in the absence of such salts. We found that less expensive and airstable Ni(acac)2 also acts as a catalyst and slightly suppresses the generation of by-product 4 (entry 12). The catalyst and LiBr loadings could be reduced to 1 mol% and 1 equiv., respectively (entry 13).