Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles
文献类型：期刊论文
| 作者 | Li, Xingwei2; Wu, Jia-Qiang1; Zhang, Shang-Shi1; Gao, Hui1; Qi, Zisong2; Zhou, Chu-Jun1; Ji, Wei-Wei1; Liu, Yao1; Chen, Yunyun1; Li, Qingjiang1 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2017-03-08 |
| 卷号 | 139期号:9页码:3537-3545 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/jacs.7b00118 |
| 文献子类 | Article |
| 英文摘要 | Fluorinated heterocycles play an important role in pharmaceutical and agrochemical industries. Herein, we report on the synthesis of four types of fluorinated heterocycles via rhodium(III)-catalyzed C-H activation of arenes/alkenes and versatile coupling with 2,2-difluorovinyl tosylate. With N-OMe benzamide being a directing group (DG), the reaction delivered a monofluorinated alkene with the retention of the tosylate functionality. Subsequent one-pot acid treatment allowed the efficient synthesis of 4-fluoroisoquinolin-1(2H)-ones and 5-fluoropyridin2(1H)-ones. When N-OPiv benzamides were used, however, [4 + 2] cyclization occurred to provide gem-difluorinated dihydroisoquinolin-1(2H)-ones. Synthetic applications have been demonstrated and the ready availability of both the arene and the coupling partner highlighted the synthetic potentials of these protocols. Mechanistically, these two processes share a common process involving N-H deprotonation, C-H activation, and olefin insertion to form a 7-membered rhodacycle. Thereafter, different reaction pathways featuring beta-F elimination and C-N bond formation are followed on the basis of density functional theory (DFT) studies. These two pathways are DG-dependent and led to the open chain and cyclization products, respectively. The mechanistic rationale was supported by detailed DFT studies. In particular, the origins of the intriguing selectivity in the competing beta-F elimination versus C-N bond formation were elucidated. It was found that beta-F elimination is a facile event and proceeds via a syn-coplanar transition state with a low energy barrier. The C-N bond formation proceeds via a facile migratory insertion of the Rh-C(alkyl) into the Rh(V) amido species. In both reactions, the migratory insertion of the alkene is turnover limiting, which stays in good agreement with the experimental studies. |
| WOS关键词 | C-H ACTIVATION ; N BOND FORMATION ; CARBON-HYDROGEN BONDS ; ONE-POT SYNTHESIS ; OXIDATIVE ANNULATION ; STEREOSELECTIVE-SYNTHESIS ; FUNCTIONAL MOLECULES ; MEDICINAL CHEMISTRY ; ARYLBORONIC ACIDS ; TANDEM CATALYSIS |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| 出版者 | AMER CHEMICAL SOC |
| WOS记录号 | WOS:000396185700035 |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/169402]  |
| 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 | Li, Xingwei; Wang, Honggen |
| 作者单位 | 1.Sun Yat Sen Univ, Sch Pharmaceut Sci, Guangzhou 510006, Guangdong, Peoples R China 2.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Li, Xingwei,Wu, Jia-Qiang,Zhang, Shang-Shi,et al. Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2017,139(9):3537-3545. |
| APA | Li, Xingwei.,Wu, Jia-Qiang.,Zhang, Shang-Shi.,Gao, Hui.,Qi, Zisong.,...&Wang, Honggen.(2017).Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,139(9),3537-3545. |
| MLA | Li, Xingwei,et al."Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139.9(2017):3537-3545. |
入库方式： OAI收割
来源：大连化学物理研究所
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。