Photocatalytic Redox-Neutral Selective Single C(sp3)–F Bond Activation of Perfluoroalkyl Imines under Redox-Neutral Conditions

Abstract Visible-light-promoted site-selective and direct C − F bond functionalization of polyfluorinated iminosulfides were accomplished with alkenes and water under redox-neutral conditions, affording a diverse array of mutifluorinated γ-lactams. A variety of perfluoroalkyl units included C 2 F 5 , C 3 F 7 , C 4 F 9 and C 5 F 11 underwent site-selective defluorofunctionlization. This protocol allows high chemoselectivity control and shows excellent functional group tolerance. Mechanistic studies reveal that the remarkable changes of the electron geometries during the defluorination widen the redox window between the substrates and the products and ensure the chemoselectivity of single C(sp 3 ) − F bond cleavage.