Dearomatization Approach to 2‑Trifluoromethylated Benzofuran and Dihydrobenzofuran Products

A mild dearomatization enabled ortho-selective replacement of an aromatic C–H bond with a hexafluoro­acetylacetone (hfacac) substituent has been developed. This reaction is dependent on a hypervalent iodine generated phenoxonium intermediate, a critical choice of solvent, and reagent addition order. The fluorinated dihydrobenzofuran product can be transformed into dihydrobenzofuran and benzofuran products decorated with a 2-trifluoromethyl group. The 3-trifluoro­methylacyl substituted benzofurans rapidly form hydrates, which can be reduced to the corresponding alcohols.