Abstract

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 CF3, CF2H 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. © 2024 The Author(s). Advanced Synthesis & Catalysis published by Wiley-VCH GmbH.