Metal promoted conversion of aromatic amines to ortho-phenylenediimine derivatives by a radical coupling path

Abstract

A radical path for the conversion of o-substituted arylamines to o-phenylenediimine derivatives is reported. In the presence of [Ru^II(PPh₃)₃Cl₂] (Ru^P), 2-(phenylthio)aniline (L^SNH₂) acts as an o-amination agent. Reaction of L^SNH₂ with Ru^P in toluene promotes (4e + 4H⁺) oxidative dimerization affording an o-phenylenediimine complex of ruthenium(II). Similarly, intermolecular coupling between L^SNH₂ and other arylamines has been achieved.