Synthesis of Sterically Hindered Dialkyl Ethers via Palladium-Catalyzed Fluoro-alkoxylation of gem -Difluoroalkenes.

Organofluorine compounds are of high value in medicinal and agricultural chemistry. Herein, we report a palladium-catalyzed fluoro-alkoxylation of gem -difluoroalkenes for the synthesis of much more challenging sterically hindered ethers. This reaction represents a direct synthesis method for α-trifluoromethyl ethers with a broad functional group tolerance and excellent regioselectivity. This system employs N -fluorobenzenesulfonimide (NFSI) as an electrophilic fluorine source and alcohols as nucleophilic donors, including but not limited to sterically hindered tert -substituted alcohols.