Photoredox-Catalyzed gem-Difluoromethylenation of Aliphatic Alcohols with 1,1-Difluoroalkenes to Access α,α-Difluoromethylene Ethers.

A switchable synthesis of alcohols and ketones bearing a CF2-OR scaffold using visible-light promotion is described. The method of PDI catalysis is characterized by its ease of operation, broad substrate scopes, and the ability to switch between desired products without the need for transition metal catalysts. The addition or absence of a base plays a key role in controlling the synthesis of the major desired products.