Copper‐Catalyzed Chloroamide‐Directed Benzylic CH Perfluoroalkylation

We report a copper‐catalyzed protocol for the regioselective benzylic C(sp 3 )H perfluoroalkylation of N ‐chloroamides using nucleophilic perfluoroalkyl reagents. This method is applicable to a wide range of substrates, enabling heptafluoropropylation and perfluorohexylation with high selectivity. Its practical utility is demonstrated through gram‐scale reactions and versatile downstream transformations. Mechanistic studies support a radical pathway involving 1,5‐hydrogen atom transfer. This efficient and mild strategy holds significant potential for applications in fluorinated drug discovery.