Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO
文献类型：期刊论文
| 作者 | Liang, Yong; Jiang, Xing; Fu, Xu-Fei; Ye, Siyu; Wang, Tao; Yuan, Jie; Wang, Yuanyuan; Yu, Zhi-Xiang |
| 刊名 | CHEMISTRY-AN ASIAN JOURNAL
 |
| 出版日期 | 2012-03-05 |
| 卷号 | 7期号:3页码:593-604 |
| 关键词 | Annulation Cycloaddition Radical Reactions Rhodium Total Synthesis |
| ISSN号 | 1861-4728 |
| DOI | 10.1002/asia.201100805 |
| 英文摘要 | The total synthesis of (+)-asteriscanolide is reported. The synthetic route features two key reactions: 1) the rhodium(I)-catalyzed [(5+2)+1] cycloaddition of a chiral ene-vinylcyclopropane (ene-VCP) substrate to construct the [6.3.0] carbocyclic core with excellent asymmetric induction, and 2) an alkoxycarbonyl-radical cyclization that builds the bridging butyrolactone ring with high efficiency. Other features of this synthetic route include the catalytic asymmetric alkynylation of an aldehyde to synthesize the chiral ene-VCP substrate, a highly regioselective conversion of the [(5+2)+1] cycloadduct into its enol triflate, and the inversion of the insideoutside tricycle to the outsideoutside structure by an ester-reduction/elimination to enol-ether/hydrogenation procedure. In addition, density functional theory (DFT) rationalization of the chiral induction of the [(5+2)+1] reaction and the diastereoselectivity of the radical annulation has been presented. Equally important is that we have also developed other routes to synthesize asteriscanolide using the rhodium(I)-catalyzed [(5+2)+1] cycloaddition as the key step. Even though these routes failed to achieve the total synthesis, these experiments gave further useful information about the scope of the [(5+2)+1] reaction and paved the way for its future application in synthesis. |
| 语种 | 英语 |
| WOS记录号 | WOS:000300871500020 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/47583]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Yu, Zhi-Xiang |
| 作者单位 | Peking Univ, Beijing Natl Lab Mol Sci BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China |
| 推荐引用方式 GB/T 7714 | Liang, Yong,Jiang, Xing,Fu, Xu-Fei,et al. Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO[J]. CHEMISTRY-AN ASIAN JOURNAL,2012,7(3):593-604. |
| APA | Liang, Yong.,Jiang, Xing.,Fu, Xu-Fei.,Ye, Siyu.,Wang, Tao.,...&Yu, Zhi-Xiang.(2012).Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO.CHEMISTRY-AN ASIAN JOURNAL,7(3),593-604. |
| MLA | Liang, Yong,et al."Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO".CHEMISTRY-AN ASIAN JOURNAL 7.3(2012):593-604. |
入库方式： OAI收割
来源：化学研究所
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