Facile, iodine-mediated access to N-aryl-2-benzoxazolamines has been achieved in a one-pot manner under mild reaction conditions. Reaction of 2-aminophenols and aryl isothiocyanates afforded N-aryl-2-benzoxazolamines in the presence of molecular iodine and pyridine in tetrahydrofuran at room temperature in moderate to excellent yields.

A facile and environmentally benign access to N-aryl/alkyl-4H-benzoxazin-2-amines is achieved from 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas under transition-metal-free conditions. The conversions occur smoothly in the presence of a catalytic amount of molecular iodine and hydrogen peroxide as the oxidant in tetrahydrofuran at room temperature to afford moderate to good yields (28–90%) of the desired products within 2 hours. This method reports the first examples of the catalytic transformations of 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas into N-aryl/alkyl-4H-benzoxazin-2-amines based on desulfurative cyclization.