Silver-Catalyzed C-C Fragmentation of Homobenzylic Alcohols: Convenient Synthesis of Fluoromethylated Arenes

A mild and practical approach to the formation of benzylic fluorides is reported via an AgBF4 -catalyzed oxidative fragmentation of acyclic homobenzylic alcohols. Following β-scission and extrusion of acetone, experimental evidence suggests that the reaction proceeds via the generation of a benzylic radical intermediate capable of reaction with Selectfluor, which acts both as fluorinating agent and oxidant for the Ag(I) catalyst. The method is amenable to the production of various fluoromethylated aromatic systems typically sensitive to oxidation such as polycyclic or electron-rich arenes.