Isolation of 3 using column chromatography on silica gel was hampered by protonation (Scheme S2). We thus investigated the corresponding triethylsilyl (TES) ether 5a, which would be less prone to protonation than the TMS ether. The catalytic reaction proceeded in the same manner as for the TMS ether (98% NMR yield) and the desired silyl fluoroenolate (6a) was isolated in 89% yield after chromatographic purification. The geometry of isolated 6a was determined to be Z using 1 H- F heteronuclear Overhauser effect spectroscopy (HOESY; Scheme S3). We confirmed that the reaction also proceeded on the gram scale to give 2.1 g of the desired product (78% yield). With the optimized reaction conditions in hand, we investigated the substrate scope of the reaction (Figure ). Aryl, alkyl, alkoxy, aniline, and fluorine substituents were tolerated under the optimal conditions to give the corresponding products (6b-6k). However, the reaction using an organozinc reagent containing the electron-withdrawing CF3 group resulted in low yield (6l). We found that benzylation (6m-6q) and methylation (6r) also proceeded in moderate to good yield. Some silyl difluoroenolates containing oxygen, nitrogen, and fluorine were also applicable for this reaction (6s-6x).