Ru-V-Acylimido Intermediate in [Ru-IV(Por)Cl-2]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions

Hong, Dan-Yan1,2; Liu, Yungen3; Wu, Liangliang1,2; Lo, Vanessa Kar-Yan1,2; Toy, Patrick H.6; Law, Siu-Man1,2; Huang, Jie-Sheng1,2; Che, Chi-Ming1,2,3,4,5

2021-05-01

10.1002/anie.202100668

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

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.

acylnitrene transfer C− N bond formation porphyrinoids ruthenium Ru-V-imido complex

SCI ; EI

英语

NI期刊

通讯

Hong Kong Research Grants Council["HKU 17301817",17304019] ; Basic Research Program-Shenzhen Fund["JCYJ20170412140251576","JCYJ20180508162429786"]

Chemistry

Chemistry, Multidisciplinary

WOS:000656372600001

WILEY-V C H VERLAG GMBH

20212310471781

Amination ; Amines ; Catalysis ; Chemical bonds ; Ketones

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1

CHEMISTRY

Web of Science

1.Univ Hong Kong, State Key Lab Synthet Chem, Pokfulam Rd, Hong Kong, Peoples R China
2.Univ Hong Kong, Dept Chem, Pokfulam Rd, Hong Kong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
4.HKU Shenzhen Inst Res & Innovat, Shenzhen 518053, Peoples R China
5.Lab Synthet Chem & Chem Biol Ltd, Units 1503-1511,15-F.,Bldg 17W, Hong Kong, Peoples R China
6.Univ Hong Kong, Dept Chem, Pokfulam Rd, Hong Kong, Peoples R China

Hong, Dan-Yan,Liu, Yungen,Wu, Liangliang,et al. Ru-V-Acylimido Intermediate in [Ru-IV(Por)Cl-2]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2021,60:18619-18629.

Hong, Dan-Yan.,Liu, Yungen.,Wu, Liangliang.,Lo, Vanessa Kar-Yan.,Toy, Patrick H..,...&Che, Chi-Ming.(2021).Ru-V-Acylimido Intermediate in [Ru-IV(Por)Cl-2]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,60,18619-18629.

Hong, Dan-Yan,et al."Ru-V-Acylimido Intermediate in [Ru-IV(Por)Cl-2]-Catalyzed C-N Bond Formation: Spectroscopic Characterization, Reactivity, and Catalytic Reactions".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60(2021):18619-18629.