A trifluoroacetate-derived reagent for trifluoromethylation of (hetero)arenes.

We report a bench-stable trifluoromethylation reagent derived from trifluoroacetic acid anhydride as a terminal CF3-source via decarboxylative Barton ester rearrangement and S-oxidation. Shifting the decarboxylation step from the trifluoromethylation process to reagent synthesis enables efficient radical trifluoromethylation under mild conditions, as demonstrated in the photocatalytic trifluoromethylation of (hetero)arenes and thiols.