C3-C3' and C6-C6' Oxidative Couplings of Carbazoles.

9-Substituted carbazoles are widely used units in materials science, and their oxidative reactions have been utilized for the synthesis and characterization of polymers. Though the oxidative mechanism of carbazoles has been known for a few decades, structural definition has remained difficult, because their polymers are generally insoluble with incomplete characterization and unknown dependence of the electrochemical potentials. The oxidative reactions of 9-substituted carbazoles should be carefully considered under specific oxidative conditions; otherwise, structure definitions could be wrong, because the IR and NMR spectra used previously cannot quantitatively analyze 3,3'-coupling and 6,6'-coupling of carbazoles. In this review, the best understanding of the C3-C3' and C6-C6' oxidative couplings of 9-substituted carbazoles is presented, and the benefit of these oxidative reactions from the viewpoints of electrochemical synthesis, film engineering, and the synthesis and processing of polymers is highlighted.