The mechanism and reactivity of Ir-catalyzed α-amidation
of 2-acylimidazoles have been investigated at the B3LYP-D3 level,
with the emphasis on nitrene insertion selectivity. The calculation
results show that the catalytic mechanism consists of iridacycle formation,
CO2 release, nitrene insertion, and amido protonation processes.
Thereinto, nitrene insertion is both rate- and selectivity-determining
steps. The origin of the nitrene group favorably inserting into an
Ir–Cα over Cγ–H bond
was further unraveled. In addition, this work also explored the α-amidation
reactivity difference between α-mono- and α,α-di-substituted
2-acylimidazoles and the source of this difference was identified.
These meaningful insights may serve as the basis for the further design
and development of transition-metal-catalyzed α-amidation systems
featuring high reactivity and selectivity.
The mechanism and chemoselectivity of Rh2-catalyzed intermolecular nitrene transfer reactions of carvone have been investigated using M06L method. By comparsions: Rh2(esp)2- vs. Rh2(OAc)4-catalysis, the origin of aziridination-to-amination chemoselectivity is revealed....
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.