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Experimental and Theoretical Studies on Rhodium-Catalyzed Coupling of Benzamides with 2,2-Difluorovinyl Tosylate: Diverse Synthesis of Fluorinated Heterocycles
Wu, Jia-Qiang1; Zhang, Shang-Shi1; Gao, Hui1; Qi, Zisong2; Zhou, Chu-Jun1; Ji, Wei-Wei1; Liu, Yao1; Chen, Yunyun1; Li, Qingjiang1; Li, Xingwei2; Wang, Honggen1
Source PublicationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY
2017-03-08
ISSN0002-7863
DOI10.1021/jacs.7b00118
Volume139Issue:9Pages:3537-3545
Indexed BySCI
SubtypeArticle
WOS HeadingsScience & Technology ; Physical Sciences
WOS SubjectChemistry, Multidisciplinary
WOS Research AreaChemistry
WOS KeywordC-H ACTIVATION ; N BOND FORMATION ; CARBON-HYDROGEN BONDS ; ONE-POT SYNTHESIS ; OXIDATIVE ANNULATION ; STEREOSELECTIVE-SYNTHESIS ; FUNCTIONAL MOLECULES ; MEDICINAL CHEMISTRY ; ARYLBORONIC ACIDS ; TANDEM CATALYSIS
AbstractFluorinated 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.
Language英语
WOS IDWOS:000396185700035
PublisherAMER CHEMICAL SOC
Citation statistics
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/169403
Collection中国科学院大连化学物理研究所
Corresponding AuthorLi, Xingwei; Wang, Honggen
Affiliation1.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
Recommended Citation
GB/T 7714
Wu, Jia-Qiang,Zhang, Shang-Shi,Gao, Hui,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 Wu, Jia-Qiang.,Zhang, Shang-Shi.,Gao, Hui.,Qi, Zisong.,Zhou, Chu-Jun.,...&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 Wu, Jia-Qiang,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.
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