Ruthenium-Catalyzed Direct C–H Amidation of Arenes: A Mechanistic Study

We report mechanistic studies of C–H activitation/amidation reactions using azides as the amino source catalyzed by [RuCl2(p-cymene)]2. We have achieved two intermediates in the catalytic cycle (C5H4NC6H4)­Ru­(p-cymene)Cl and (C5H4NC6H4)­NArRu­(p-cymene)Cl (Ar = NO2C6H4SO2). Furthermore, the process from (C5H4NC6H4)­Ru­(p-cymene)Cl to (C5H4NC6H4)­NArRu­(p-cymene)Cl was monitored by 19F NMR and a ruthenium–imido species was proposed to explain the formation of the azacyclopropane analogue.