Oxidative Coupling of Carbazoles: A Substituent-Governed Regioselectivity Profile

Oxidative C-C coupling of carbazoles possessing various substituents is demonstrated in the presence of organic (metal-free) recyclable oxidants, such as DDQ or CA/H⁺, for accessing bicarbazole regioisomers. Differently substituted carbazoles are examined to showcase regioselective discrimination (3,3'- versus 1,3'-bicarbazoles) and preferences based on sterics and electronics in oxidative coupling. Finally, a mechanism that involves the carbazole radical cation has been traced (evidenced) and proposed on the basis of the UV-vis-NIR absorption and EPR spectroscopy results. This study underlines the strategic chemical preparation of a series of bicarbazoles in an efficient manner.