Iodine(III)-Catalyzed Oxidative Cyclization of Aryl Amines to Construct N -Alkylbenzimidazoles.

An I(III)-catalyzed oxidative cyclization reaction using selectfluor as the oxidant was developed that converts ortho -substituted anilines to benzimidazoles. The mild reaction requires as little as 0.5 mol % of iodobenzene, and its scope is broad: electron-withdrawing or electron-releasing groups on the aniline portion are tolerated, and cyclic or acyclic N -alkylamines are permitted as ortho -substituents. Preliminary mechanistic investigations suggest that benzimidazole formation occurs via cationic reactive intermediates, and an intramolecular kinetic isotope effect of 1.98 ± 0.05 was measured.