Synthesis of Aryl Difluoroalkyl Ethers by Deprotonative Functionalization of the Difluoromethoxy (OCHF ₂ ) Moiety

An unprecedented deprotonative functionalization of difluoromethoxylated compounds is described herein using a lithiated base under in situ trapping conditions. Aryl α , α ‐difluoroalkyl ethers could be obtained in a two‐step process via difluoro(trimethylsilyl)methylated compounds without any intermediate purification. These new silylated scaffolds act as intermediates to mask the highly unstable difluorinated carbanion and to limit the formation of fluorocarbenes. Desilylative trapping with various electrophiles using a fluoride source gave rise to a library of new α , α ‐difluorinated ethers, which could be of particular interest in various fields such as life sciences or materials chemistry.