Oxalates as Activating Groups for Tertiary Alcohols in Photoredox-Catalyzed gem-Difluoroallylation To Construct All-Carbon Quaternary Centers

Construction of challenging and important all-carbon quaternary centers has received growing attention. Herein, with oxalates as activating groups for tertiary alcohols, we report photoredox-catalyzed gem-difluoroallylation to construct all-carbon quaternary centers enabled by efficient tertiary radical addition to α-trifluoromethyl alkenes. This transformation shows good functional group tolerance for both α-trifluoromethyl alkenes and oxalates. Moreover, this strategy is also successfully applied to the synthesis of monofluoralkenes from the corresponding electron-rich gem-difluoroalkenes and cesium tertiary alkyl oxalates under modified conditions.