Fe-LMCT Photodecarboxylation for (Hetero)arene Chloro- and Bromodifluoromethylation: Rapid Access to Aromatic Acyl Fluorides

Chloro- and bromodifluoromethyl groups (CF₂X) offer complementary properties to other fluorinated substituents in modulating biological functionality and provide versatile synthetic handles for postfunctionalization. However, their widespread use remains limited by the scarcity of practical halodifluoromethylating reagents. Here, we report a photoinduced Fe-catalyzed strategy that repurposes readily available chloro- and bromodifluoroacetates as traceless radical precursors for (hetero)arene C-H halodifluoroalkylations. The resulting products exhibit broad synthetic versatility, enabling streamlined one-pot access to valuable acyl fluoride synthons.