Transition Metal‐Free Homocoupling of Unactivated Electron‐Deficient Azaarenes

Abstract This work has established the first direct homocoupling of unactivated electron‐deficient azaarenes in the presence of TMPMgCl (2,2,6,6‐tetramethylpiperidinylmagnesium chloride) and TMEDA (tetramethylethylenediamine). In this process, no transition metal was used while freely available air was employed as the oxidant. The investigated successful substrates included quinolines, isoquinoline, 3‐phenylated pyridines, and 2‐phenylated quinoxalines, giving moderate to high yields. The homocoupling of quinolines was effectively scaled up to one gram in high yield. Additionally, an iridium complex of 6,6′‐dimethyl‐2,2′‐biquinoline was prepared and characterized as an efficient red‐emitting material. magnified image