Construction of gem-Difluoroenol Esters through Catalytic O-Selective Addition of Difluoroenoxysilanes to Ketenes

The O-site reactivity of difluoroenoxysilanes is disclosed for the first time, which enabled the direct construction of versatile gem-difluoroalkenes through an unprecedented highly efficient addition reaction with ketenes. A series of valuable gem-difluoroenol esters were achieved in good to excellent yields. The synthetic versatility of this protocol is further demonstrated by the gram-scale synthesis and good functional group tolerance.