Radical Fluoroalkoxylation of α-Mono/Trihalo Ketones.

Herein we report a photocatalytic radical fluoroalkoxylation of α-mono/trihalo ketones via selective C-X (X = F, Cl, Br) bond activation. The protocol affords diverse α,α-difluoromonofluoromethoxy ketones from readily available α-halo ketones under mild conditions with broad substrate scope and excellent functional group tolerance. It is amenable to one-pot synthesis and late-stage diversification of pharmaceuticals and bioactive molecules. The strategy is further applicable to trifluoroethoxylation and alkoxylation, demonstrating the versatility of this radical fluoroalkoxylation platform. Mechanistic studies, including EPR and radical-trapping experiments, support an O-centered radical pathway.