Sulfate Radical Anion (SO4 •–) Mediated C(sp3)–H Nitrogenation/Oxygenation in N‑Aryl Benzylic Amines Expanded the Scope for the Synthesis of Benzamidine/Oxazine Heterocycles

A transition-metal-free, K2S2O8-mediated intramolecular oxidative nitrogenation/oxygenation of C­(sp3)–H in N-aryl benzylic amines followed by oxidation at the benzylic center has been developed for the synthesis of benzamidine/benzoxazine heterocycles, providing an expedient access to quinazolin-4­(3H)-ones, N-aryl-2-arylbenzimidazoles, and 4H-3,1-benzoxazin-4-ones. A considerable amount of work dealing with the mechanistic study to understand the crucial intramolecular cyclization step largely favors an iminium ion as the key intermediate.