Photoredox‐Catalyzed Defluorinative Functionalizations of Polyfluorinated Aliphatic Amides and Esters

Abstract Selective C−F bond functionalization of perfluoalkyl units has huge potential towards accessing functionalized organofluorinated compounds, but remains challenging due to the high C−F bond strength and inherent selectivity challenges. We report a new catalytic approach to the selective functionalization of strong C−F bonds in polyfluorinated aliphatic esters and amides. This simple reaction proceeds in mild and operational fashion with divergent conversions, including hydrodefluorination, defluoroalkylation, and defluoroalkenylation, affording a diverse array of important partially fluorinated motifs. Straightforward downstream chemistry towards fluorinated alcohols, amines and drug derivatives highlights the potential of the protocol.