RuV-Acylimido Intermediate in [RuIV(Por)Cl2]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Metal-catalyzed C-N bond formation reactions via acylnitrene transfer have recently attracted much attention, but direct detection of the proposed acylnitrenoid/acylimido M(NCOR) (R=aryl or alkyl) species in these reactions poses a formidable challenge. Herein, we report on Ru(NCOR) intermediates in C-N bond formation catalyzed by [Ru-IV(Por)Cl-2]/N3COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, alpha-amino ketone formation from silyl enol ethers, amination of C(sp(3))-H bonds, and functionalization of natural products and carbohydrate derivatives (up to 99 % yield). Experimental studies, including HR-ESI-MS and EPR measurements, coupled with DFT calculations, lend evidence for the formulation of the Ru(NCOR) acylnitrenoids as a Ru-V-imido species.

Automated summary

This study reports on Ru(NCOR) intermediates in C-N bond formation catalyzed by [Ru-IV(Por)Cl-2]/N3COR, which is applicable to various chemical reactions with high yields. Experimental studies and DFT calculations support the formulation of Ru(NCOR) acylnitrenoids as a Ru-V-imido species.