N-Sulfonylaminophthalimide-Catalyzed Aerobic Oxidative Cleavage of α-C(sp3)-H and β,γ-C(sp3)-C(sp3) Bonds of Tertiary Amines.

A N-sulfonylaminophthalimide (NSAPI)-catalyzed one-stop solution for aerobic oxidization of tertiary amine, including α-C-H carbonylation and β,γ-C-C bond cleavage, under mild conditions was reported, affording the corresponding formamide in moderate to excellent yields. The protocol exhibits broad substrate scope, tolerating a wide range of tertiary anilines, aryl morpholines, and piperazine derivatives with various electronic and steric properties. Mechanistic studies, including radical trapping experiments and HRMS analysis, support a radical-mediated pathway initiated by deprotonation and oxidation of NSAPI, followed by α-C-H hydrogen atom abstraction, peroxyl radical formation, and subsequent C-C bond scission.