NIS‐Mediated Intramolecular sp3 C−H Oxidation of 2‐Alkyl‐Substituted Benzamides

In this work, we describe the N‐iodosuccinimide‐mediated benzyl sp3 C−H oxidation of 2‐alkyl‐substituted benzamide derivatives. This Hofmann‐Löffler‐Freytag (HLF) type reaction involving intramolecular sp3 C−O bond formation differs from the construction of the C−N bond in the classic and modified HLF reactions. This reaction proceeded smoothly via 1,5‐hydrogen atom transfer of N‐centered radicals directly afforded by in situ N−I bond generation, providing iminoisobenzofuran derivatives in moderate to excellent yields with exclusive chemoselectivity. A new N‐iodosuccinimide‐mediated intramolecular oxidation to construct C−O bonds has been developed. The reaction differs in the construction of the C−N bond from the classic and modified Hofmann‐Löffler‐Freytag reactions.