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

Dan-Yan Hong; Yungen Liu; Liangliang Wu; Vanessa Kar-Yan Lo; Patrick H Toy; Siu-Man Law; Jie-Sheng Huang; Chi-Ming Che

doi:10.1002/anie.202100668

Ru^V -Acylimido Intermediate in [Ru^IV (Por)Cl₂ ]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Angew Chem Int Ed Engl. 2021 Aug 16;60(34):18619-18629. doi: 10.1002/anie.202100668. Epub 2021 May 31.

Authors

Dan-Yan Hong¹, Yungen Liu², Liangliang Wu¹, Vanessa Kar-Yan Lo¹, Patrick H Toy³, Siu-Man Law¹, Jie-Sheng Huang¹, Chi-Ming Che^{1

2

4

5}

Affiliations

¹ State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China.
² Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, 518055, China.
³ Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong SAR, China.
⁴ HKU Shenzhen Institute of Research and Innovation, Shenzhen, 518053, China.
⁵ Laboratory for Synthetic Chemistry and Chemical Biology Limited, Units 1503-1511, 15/F., Building 17W, Hong Kong Science and Technology Parks, New Territories, Hong Kong SAR, China.

PMID: 33847064
DOI: 10.1002/anie.202100668

Abstract

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)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 Ru^V -imido species.

Keywords: C−N bond formation; RuV-imido complex; acylnitrene transfer; porphyrinoids; ruthenium.

Publication types

Research Support, Non-U.S. Gov't