Photocatalyzed Aryl C‐H Fluorocarbonylation with CF₂Br₂

Abstract The use of abundant and inexpensive fluorine feedstocks to synthesize fluorinated compounds is a promising strategy that has not been extensively investigated. Dibromodifluoromethane (CF 2 Br 2 ) is an inexpensive fluorine source that has rarely been used for C−H fluoroalkylation. This study reveals an iridium‐catalyzed, tunable strategy for synthesizing acyl fluorides and difluorobromomethylated products using CF 2 Br 2 . To achieve the desired products, this process only requires the change of solvent (from DMSO to 1,4‐dioxane) under blue LED illumination. A variety of arenes and heteroarenes with electron‐donating substituents were successfully used, yielding the corresponding products in moderate to good yields. Mechanistic experiments revealed that DMSO served a dual role, functioning as both solvent and nucleophilic reagent in C−H fluorocarbonylation.