Rh(II)-Catalyzed Selective C(sp3)-H/C(sp2)-H Bonds Cascade Insertion to Construct [6-8-6] Benzo-Fused Scaffold
文献类型：期刊论文
| 作者 | Yu, Tao3,4; Fang, Feifei2; Shou, Haowen4; Li, Yazhou1; Qu, Zhiyan3,4; Chen, Feiyang2; Zhang, Yu2; Wang, Jiang2,4 ; Liu, Hong2,3,4
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| 刊名 | ORGANIC LETTERS
 |
| 出版日期 | 2024-12-10 |
| 卷号 | 26期号:50页码:10719-10728 |
| ISSN号 | 1523-7060 |
| DOI | 10.1021/acs.orglett.4c03619 |
| 英文摘要 | The fused eight-membered carbocycles (EMCs) play vital roles in the medicinal and biological investigations of many natural products and marketed drugs. The traditional synthesis of [6-8-6] benzo-fused derivatives involves multistep reactions and low yields, making the development of a one-step synthesis method a more challenging work. Here, we present a novel strategy for one-step construction of [6-8-6] benzo-fused scaffold from propargyl diazoacetates substituted with benzyl-nitrogen heterocyclic ring via Rh(ll)-catalyzed carbene/alkyne metathesis (CAM) and selective C-H bond insertion. This method exhibits a specific substrate scope, simple operation, mild reaction conditions, and high atom efficiency. Mechanistically, the process involves sequential CAM, 1,3-H-shift, intramolecular nucleophilic attack, and selective C(sp3)-H/C(sp2)-H bonds cascade insertion. Notably, the unique spirocyclic zwitterionic intermediate generated in this sequence contributes to N-heterocycle migration and fused eight-membered carbocycle formation. Additionally, the C(sp3)-H bond insertion connected to the oxygen atom rather than the nitrogen atom has been unexpectedly confirmed with the assistance of the spirocyclic zwitterionic intermediate. Overall, our findings open up a new avenue for the construction of [6-8-6] benzo-fused scaffold. |
| WOS关键词 | CATALYZED CARBENE/ALKYNE METATHESIS ; RING ; FLUORINE ; FUNCTIONALIZATION ; ARYLDIAZOACETATES ; CYCLOPENTADIENES ; CYCLOADDITION ; REARRANGEMENT ; CYCLIZATION ; ANNULATION |
| 资助项目 | National Natural Science Foundation of China[2022YFA1302900] ; National Key R&D Program of China[82130105] ; National Key R&D Program of China[22337003] ; National Key R&D Program of China[82121005] ; National Key R&D Program of China[22177124] ; National Key R&D Program of China[82322063] ; National Key R&D Program of China[LG-GG-202204-02] ; National Natural Science Foundation of China[23XD1460300] ; Program of Shanghai Academic Research Leader[2022231] ; Shanghai Postdoctoral Excellence Program[22YF1460700] ; Shanghai Sail Program |
| WOS研究方向 | Chemistry |
| WOS记录号 | WOS:001375041400001 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://119.78.100.183/handle/2S10ELR8/315049]  |
| 专题 | 新药研究国家重点实验室 |
| 通讯作者 | Wang, Jiang; Liu, Hong |
| 作者单位 | 1.UCAS, Hangzhou Inst Adv Study, Sch Pharmaceut Sci & Technol, Hangzhou 310024, Peoples R China 2.Lingang Lab, Shanghai 200031, Peoples R China 3.Univ Chinese Acad Sci, Sch Pharm, Beijing 100049, Peoples R China 4.Chinese Acad Sci, Shanghai Inst Mat Med, State Key Lab Drug Res, Shanghai 201203, Peoples R China |
| 推荐引用方式 GB/T 7714 | Yu, Tao,Fang, Feifei,Shou, Haowen,et al. Rh(II)-Catalyzed Selective C(sp3)-H/C(sp2)-H Bonds Cascade Insertion to Construct [6-8-6] Benzo-Fused Scaffold[J]. ORGANIC LETTERS,2024,26(50):10719-10728. |
| APA | Yu, Tao.,Fang, Feifei.,Shou, Haowen.,Li, Yazhou.,Qu, Zhiyan.,...&Liu, Hong.(2024).Rh(II)-Catalyzed Selective C(sp3)-H/C(sp2)-H Bonds Cascade Insertion to Construct [6-8-6] Benzo-Fused Scaffold.ORGANIC LETTERS,26(50),10719-10728. |
| MLA | Yu, Tao,et al."Rh(II)-Catalyzed Selective C(sp3)-H/C(sp2)-H Bonds Cascade Insertion to Construct [6-8-6] Benzo-Fused Scaffold".ORGANIC LETTERS 26.50(2024):10719-10728. |
入库方式： OAI收割
来源：上海药物研究所
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