SIOC OpenIR  > 金属有机化学国家重点实验室
Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination
Alternative Title非正常卡宾银络合物的合成, 活性及氧化氟化机理研究
Liu QL(刘启伦)1; Yuan ZL(袁浙梁)1; Wang HY(王昊阳)1; Li Y(李阳)1; Wu YC(吴奕晨)1; Leng XB(冷雪冰)1; Chen PH(陈品红)1; Guo YL(郭寅龙)1; Lin ZY(林振阳)1; Liu GS(刘国生)1
2015
Source PublicationACS Catal.
Volume5Issue:11Pages:6732-6737
AbstractA silver-catalyzed intramolecular amination of alkynl-imine substrates has been extensively studied to build various isoquinoline derivatives efficiently. However, most of these transformations are limited to hydroamination, and the related oxidative reaction is quite rare. Importantly, the mechanistic details are still unknown, which retarded further progress in the field. In this work, a novel abnormal mesoionic carbene silver complex (MIC)(n)Ag(I) was isolated and fully characterized as the key intermediate. Further investigation on the oxidative transformation of the silver complex reveals that successful oxidative halogenation could be achieved with NXS (X = Cl, Br, and I), as well as F+ reagent. Surprisingly, the fluorination reaction occurred in the presence of both strong (SelectFluor) and weak (NFSI) fluorinating reagents, although the F-Py-type reagent, whose oxidative potential lies between, is ineffective. Further mechanistic studies disclosed that (1) from kinetic data, the (MIC)Ag(I) complex was proved to be the reactive intermediate in the fluorination reaction, and pyridyl-oxazoline (Pyox) ligand could significantly improve this transformation; (2) from DFT calculation results, two different mechanistic pathways were suggested to be involved, a metathesis process in the case of NFSI promoted by the chelation of sulfonyl group toward the silver center and a redox process in the case of SelectFluor due to its strong oxidative potential.
Subtype论文
Subject Area金属有机化学
DOI10.1021/acscatal.5b01885
URL查看原文
Indexed BySCI
Language英语
WOS IDWOS:000364441300061
Citation statistics
Cited Times:9[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/39654
Collection金属有机化学国家重点实验室
Corresponding AuthorWang HY(王昊阳); Lin ZY(林振阳); Liu GS(刘国生)
Affiliation1.中科院上海有机化学研究所, 金属有机化学国家重点实验室
2.香港科技大学
Recommended Citation
GB/T 7714
Liu QL,Yuan ZL,Wang HY,et al. Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination[J]. ACS Catal.,2015,5(11):6732-6737.
APA 刘启伦.,袁浙梁.,王昊阳.,李阳.,吴奕晨.,...&刘国生.(2015).Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination.ACS Catal.,5(11),6732-6737.
MLA 刘启伦,et al."Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination".ACS Catal. 5.11(2015):6732-6737.
Files in This Item:
File Name/Size DocType Version Access License
2015571.pdf(1385KB)期刊论文作者接受稿开放获取CC BY-NC-SAApplication Full Text
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Google Scholar
Similar articles in Google Scholar
[刘启伦]'s Articles
[袁浙梁]'s Articles
[王昊阳]'s Articles
Baidu academic
Similar articles in Baidu academic
[刘启伦]'s Articles
[袁浙梁]'s Articles
[王昊阳]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[刘启伦]'s Articles
[袁浙梁]'s Articles
[王昊阳]'s Articles
Terms of Use
No data!
Social Bookmark/Share
All comments (0)
No comment.
 

Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.