Abnormal Mesoionic Carbene Silver Complex: Synthesis, Reactivity, and Mechanistic Insight on Oxidative Fluorination
文献类型：期刊论文
| 作者 | 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 |
| 刊名 | ACS Catal.
 |
| 出版日期 | 2015 |
| 卷号 | 5期号:11页码:6732-6737 |
| 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 |
| 通讯作者 | 王昊阳 ; 林振阳 ; 刘国生 |
| 英文摘要 | 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. |
| 学科主题 | 金属有机化学 |
| 收录类别 | SCI |
| 原文出处 | http://dx.doi.org/10.1021/acscatal.5b01885 |
| 语种 | 英语 |
| WOS记录号 | WOS:000364441300061 |
| 源URL | [http://ir.sioc.ac.cn/handle/331003/39654]  |
| 专题 | 上海有机化学研究所_金属有机化学国家重点实验室 |
| 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 |
| 推荐引用方式 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. |
入库方式： OAI收割
来源：上海有机化学研究所
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