Iodine is shown to be an efficient catalyst for a one-step, three-component aza-Friedel– Crafts reaction of activated arenes or heteroarenes with benzyl or tert-butyl carbamates in combination with a wide variety of aldehydes in toluene under 'open-flask'and mild conditions. In the presence of 5mol% of iodine in toluene at room temperature, the reaction gives the corresponding N-CBz or N-Boc protected α-branched amines, selectively, in ...