Insights into gold-catalyzed formation of aza-heterocycles using benzofuroxans as nitrene transfer reagents: mechanism and origins of chemoselectivity

Density functional theory (DFT) calculations have been performed to reveal the mechanism of gold(i)-catalyzed annulation of N-allylynamides and benzofuroxans as nitrene transfer reagents to construct azaheterocyclic compounds. The calculated results revealed that the reaction mechanism mainly undergoes eight processes. Among the reaction steps, intramolecular nucleophilic attack of the imino N atom on the α-position of activated gold keteniminium is a rate-determining process, which is different from that proposed previously by experiment. The chemoselectivity of the products is controlled by competition between the cyclopropanation of α-imino gold carbenes and intramolecular nucleophilic attack of the phenyl ring on α-imino gold carbenes, and could be explained by NPA charge. The different yields of cyclopropanated product in different solvents are dictated by the relative polarity leading to the different energy barriers of the rate-determining steps. The present work expounds the experimental observation at the molecular level and is informative for exploring efficient syntheses of 3-azabicyclo[3.1.0]hexanes.