Photocatalytic Functionalization of Alkenes Enabled by Polyfluoroaryl Migration

Abstract Visible light‐mediated photocatalytic approach for the radical functionalization of alkenes bearing the fluorinated aryl sulfide fragment is described. The process occurs in the presence of organic photocatalyst using sulfinates as sources of radicals. The key step of the reaction is the intramolecular 1,4‐migration of the polyfluoroaryl group. In the reaction, three new bonds are formed (two C−C and one C−S bond). The decisive role of fluorine atoms in the reaction efficiency was confirmed by DFT calculations.