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

An I(III)-catalyzed oxidative cyclization reaction using selectfluor as the oxidant was developed that converts -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 -alkylamines are permitted as -substituents.

Iodine(III)-Mediated Oxidation of Anilines to Construct Dibenzazepines.

The development of an efficient process that produces bioactive medium-sized N-heterocyclic scaffolds from 2-substituted anilines using either iodosobenzene or (bis(trifluoroacetoxy)iodo)-benzene is reported. The tether between the sulfonamide and the aryl group can be varied to access dihydroacridine-, dibenzazepine-, or dibenzazocine scaffolds. While substitution on the aniline portion is limited to electron-neutral- or electron-poor groups, a broader range of functional groups are tolerated on the ortho-aryl substituent and site selective C-NAr bond formation can be achieved.