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Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination
其他题名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
发表期刊ACS Catal.
卷号5期号:11页码:6732-6737
摘要A 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.
文章类型论文
学科领域金属有机化学
DOI10.1021/acscatal.5b01885
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收录类别SCI
语种英语
WOS记录号WOS:000364441300061
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被引频次:8[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/39654
专题金属有机化学国家重点实验室
通讯作者Wang HY(王昊阳); Lin ZY(林振阳); Liu GS(刘国生)
作者单位1.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
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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.
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