Hydrofluoroether Synthesis through One‐Pot Anodic Iodoalkoxylation of Alkenes

The incorporation of carbon‐fluorine bonds can profoundly influence the chemical and physical properties of drugs, agrochemicals, and materials. Different methods allow the installation of CF 3 , CF 2 H units and C−F bonds including trifluoro‐ and difluoromethoxylations, reflecting the limited diversity of reactions available to synthetic chemists. We introduce the 2,2,2‐trifluoroethoxy group through an electro‐oxidative iodination of alkenes as a versatile substituent for fluorine chemists. An iodoarene serves as an unusual iodine source facilitating the 1,2‐iodoalkoxylation of a broad range of industrially relevant aliphatic alkenes in high yields (31–98%) showing high Markovnikov regioselectivity.