Stereoselective construction of an unprecedented 7-8 fused ring system in micrandilactone a by [3,3]-sigmatropic rearrangement.
Stereoselective construction of an unprecedented 7-8 fused ring system in micrandilactone a by [3,3]-sigmatropic rearrangement.
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DOI：
10.1021/ol703126q
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发表时间：
2008-01
期刊：
影响因子：
5.2
通讯作者：
Yandong Zhang;W. Ren;Y. Lan;Q. Xiao;Kai Wang;Jie Xu;Jia-Hua Chen;Zhen Yang
中科院分区：
文献类型：
--
作者：
Yandong Zhang;W. Ren;Y. Lan;Q. Xiao;Kai Wang;Jie Xu;Jia-Hua Chen;Zhen Yang
通过Bu_3Al促进的Claisen重排反应，构建了具有所需立体化学结构和功能基团的7-8双环结构的甘草内酯A（1）。计算结果表明，环外乙烯基醚通过椅状过渡态经历了[3，3] σ转移过程，在新生成的8元环中只提供Z-双键，具有高水平的手性转移.
The 7-8 bicyclic ring system of micrandilactone A (1) with the required stereochemistry and functional groups was constructed by a Bu3Al-promoted Claisen rearrangement. Computational studies indicated that the exocyclic vinyl ether undergoes a [3,3] sigmatropic process via a chairlike transition state to afford exclusively the Z-double bond in the newly generated 8-membered ring with a high level of chirality transfer.