In this paper, a fluoro‐hydroxylation of gem‐difluoroalkenes is demonstrated. This protocol uses sequential electrophilic fluorination with Selectfluor and nucleophilic hydroxylation with H218O, which can be used to prepare 18O‐labeled α‐CF3 alcohols from gem‐difluorostyrenes. The reaction is typically carried out at room temperature within 4 h in good to excellent yields. Other nucleophiles (besides H218O), such as alcohols, carboxylic acid, acetonitrile and N,N‐dimethylformamide, are also suitable for this difunctionalization of gem‐difluoroalkenes.

Trifluoromethyl phenyl sulfone is traditionally a nucleophilic trifluoromethylating agent. Herein, we report the first example of the use of trifluoromethyl phenyl sulfone as a trifluoromethyl radical precursor. Arylthiolate anions can...