Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond
文献类型：期刊论文
| 作者 | Wang, Qiang1; Li, Yingzi2; Qi, Zisong1; Xie, Fang1; Lan, Yu2; Li, Xingwei1 |
| 刊名 | ACS CATALYSIS
 |
| 出版日期 | 2016-03-01 |
| 卷号 | 6期号:3页码:1971-1980 |
| 关键词 | C-h Bond Activation Rh(Iii) Catalyst N-s Bond Cleavage N-sulfinyl Imine Olefin Isoindole |
| ISSN号 | 2155-5435 |
| DOI | 10.1021/acscatal.5b02297 |
| 文献子类 | Article |
| 英文摘要 | C-H activation under redox-neutral conditions, especially by Rh(III) catalysis, has offered attractive synthetic strategies. Previous work in redox-neutral C-H activation relied heavily on the cleavage of oxidizing N-O and N-N directing groups, and cleavable N-S bonds have been rarely used, although they may offer complementary coupling patterns. In this work, N-sulfinyl ketoimines were designed as a novel substrate for the redox-neutral coupling with different activated olefins via a Rh-catalyzed C-H activation pathway. The coupling with acrylate esters afforded 1H-isoindoles with the formation of three chemical bonds around a quaternary carbon. Furthermore, the coupling with maleimides furnished pyrrolidone-fused isoquinolines. A broad scope of substrates has been established. The mechanism of the coupling with acrylates has been studied in detail by a combination of experimental and computational methods. This coupling proceeds via imine-assisted C-H activation of the arene followed by ortho C-H olefination to afford a Rh(III) olefin hydride intermediate which, upon deprotonation, may exist in equilibrium with a Rh(I) olefin species. Cleavage of the N-S bond occurs only after C-H olefination to generate a Rh(III) imide species. DFT studies indicated that the imide group can undergo migratory insertion to produce a Rh(III) secondary alkyl which isomerizes under the assistance of acetic acid to a Rh(III) tertiary alkyl that is prone to insertion of the second acrylate. |
| WOS关键词 | SUBSTITUTED PYRIDINE-DERIVATIVES ; RHODIUM-CATALYZED SYNTHESIS ; OXYGEN-ATOM TRANSFER ; SULFONIC-ACID GROUP ; ONE-POT SYNTHESIS ; DIRECTING GROUP ; INTERNAL OXIDANT ; REGIOSELECTIVE SYNTHESIS ; INDOLE SYNTHESIS ; EFFICIENT SYNTHESIS |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000371755500067 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/171072]  |
| 专题 | 大连化学物理研究所_中国科学院大连化学物理研究所 |
| 通讯作者 | Lan, Yu; Li, Xingwei |
| 作者单位 | 1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China 2.Chongqing Univ, Sch Chem & Chem Engn, Chongqing 400030, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang, Qiang,Li, Yingzi,Qi, Zisong,et al. Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond[J]. ACS CATALYSIS,2016,6(3):1971-1980. |
| APA | Wang, Qiang,Li, Yingzi,Qi, Zisong,Xie, Fang,Lan, Yu,&Li, Xingwei.(2016).Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond.ACS CATALYSIS,6(3),1971-1980. |
| MLA | Wang, Qiang,et al."Rhodium(III)-Catalyzed Annulation between N-Sulfinyl Ketoimines and Activated Olefins: C-H Activation Assisted by an Oxidizing N-S Bond".ACS CATALYSIS 6.3(2016):1971-1980. |
入库方式： OAI收割
来源：大连化学物理研究所
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