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 [RuIV (Por)Cl2 ]/N3 COR, a catalytic method applicable to aziridine/oxazoline formation from alkenes, amination of substituted indoles, α-amino ketone formation from silyl enol ethers, amination of C(sp3 )-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 RuV -imido species.