Redox system for perfluoroalkylation of arenes and α-methylstyrene derivatives using titanium oxide as photocatalyst

Abstract

Photoirradiation of titanium oxide (TiO 2) excites the electrons from the valence band to the conduction band, leaving holes in the valence band. Using these holes and electrons, it is possible to perform one-electron oxidations and reductions. We developed a method for the photocatalytic perfluoroalkylation of aromatic rings such as benzene and its derivatives, naphthalene and benzofuran with perfluoroalkyl iodide by the combination of reduction and oxidation reactions with TiO 2. Perfluoroalkyl iodide was reduced to a perfluoroalkyl radical by the excited electrons in the conduction band of TiO 2, and the resulting radical reacted with an aromatic ring to form an arenium radical that was successively oxidized to a cation by the holes in the valence band of TiO 2. Similarly, the photocatalytic reaction of α-methylstyrene with perfluoroalkyl iodide afforded perfluoroalkylated α-methylstyrene, in which the perfluoroalkyl group is on a methyl carbon.