Intramolecular Metal‐Free Oxidative Aryl–Aryl Coupling: An Unusual Hypervalent‐Iodine‐Mediated Rearrangement of 2‐Substituted <i>N</i>‐Phenylbenzamides

Abstract

Abstract Hypervalent‐iodine‐mediated oxidative coupling of the two aryl groups in either 2‐acylamino‐ N ‐phenyl‐benzamides or 2‐hydroxy‐ N ‐phenylbenzamides, with concomitant insertion of the ortho ‐substituted N or O atom into the tether, has been described for the first time. This unusual metal‐free rearrangement reaction involves an oxidative C(sp 2 )C(sp 2 ) aryl–aryl bond formation, cleavage of a C(sp 2 )C(O) bond, and a lactamization/lactonization. Furthermore, unsymmetrical diaryl compounds can be easily obtained by removing the tether within the cyclized product.