Intramolecular Metal-Free Oxidative Aryl-Aryl Coupling: An Unusual Hypervalent-Iodine-Mediated Rearrangement of 2-Substituted N-Phenylbenzamides

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(sp2)C(sp2) aryl–aryl bond formation, cleavage of a C(sp2)C(O) bond, and a lactamization/lactonization. Furthermore, unsymmetrical diaryl compounds can be easily obtained by removing the tether within the cyclized product. Making (re)arrangements: 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 is described. This unusual metal‐free rearrangement reaction involves an oxidative C(sp2)C(sp2) aryl–aryl bond formation, cleavage of a C(sp2)C(O) bond, and a lactamization/lactonization.