Iron-Catalyzed Photochemical Defluorinative Functionalization of Polyfluorinated Aromatics.

Iron photocatalysis has emerged as a sustainable platform for C-H functionalization. This study describes a photocatalytic strategy for the selective defluorinative functionalization of polyfluorinated aromatics. The developed methodology enables selective defluorosulfonylation with sulfur dioxide and defluorinative alkylation with alkanes under visible light irradiation. Additionally, direct defluorinative functionalization with carboxylic acids has been achieved. These protocols demonstrate excellent site-selectivity and broad substrate scope, tolerating diverse functional groups, including cyano, acetyl, ester, and trifluoromethyl substituents. Notably, the methodology is compatible with drug-like molecules containing complex structures, thereby expanding the synthetic utility of iron photocatalysis in the construction of complex polyfluorinated molecules.