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.

N-Hydroxyphthalimide/benzoquinone-catalyzed chlorination of hydrocarbon C-H bond using N-chlorosuccinimide.

The direct chlorination of C-H bonds has received considerable attention in recent years. In this work, a metal-free protocol for hydrocarbon C-H bond chlorination with commercially available N-chlorosuccinimide (NCS) catalyzed by N-hydroxyphthalimide (NHPI) with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) functioning as an external radical initiator is presented. Aliphatic and benzylic substituents and also heteroaromatic ones were found to be well tolerated. Both the experiments and theoretical analysis indicate that the reaction goes through a process wherein NHPI functions as a catalyst rather than as an initiator. On the other hand, the hydrogen abstraction of the C-H bond conducted by a PINO species rather than the highly reactive N-centered radicals rationalizes the high chemoselectivity of the monochlorination obtained by this protocol as the latter is reactive towards the C(sp3)-H bonds of the monochlorides. The present results could hold promise for further development of a nitroxy-radical system for the highly selective functionalization of the aliphatic and benzylic hydrocarbon C-H.