Site‐Selective C‐Alkylation of Fluoroamides with Active Methylene Compounds

Here, switchable site‐ and chemo‐selectivity was achieved in the α‐ and δ‐C(sp3)–H alkylation of fluoroamides with active methylene compounds by leveraging different activation modes. The α‐alkylation was facilitated by a base‐promoted, catalyst‐free selective activation of fluoroamides, while the δ‐alkylation occurred through copper‐catalyzed formation of C‐centered radicals via HAT from unactivated δ‐C‐H bonds by N‐centered radicals. Furthermore, each of these scalable techniques is notable for its good functional group tolerance and a wide substrate scope.