倍半萜chloranthalactone A和F的全合成

赵刚

摘要：采用仿生生源合成策略，金粟兰内酯（+）-chloranthalactone F被首次合成。探索了如何构建（+）-chloranthalactone F 的生源前体3/5/6三环不饱和内酯（+）-chloranthalactone A。从（R）-Hajos-Wiechert酮出发，选择性合成了热力学不稳定的反式氢化茚酮，经Wharton 转化和 Simmons-Smith环丙烷化等关键步骤，制备了3/5/6三环不饱和内酯（+）-chloranthalactone A，最终经[2+2]仿生途经完成了首次（+）-chloranthalactone F全合成。该工作揭示了（+）-chloranthalactone F的生源合成途径以及确定其绝对构型。

关键词：全合成；倍半萜；chloranthalactone A； chloranthalactone F

Total synthesis of sesquiterpenoid chloranthalactone A and F

Abstract：Total synthesis of （+）-chloranthalactone F was first been accomplished via biomimetic synthetic strategies. Firstly， the synthetic strategies to the unsaturated lactones and the construction of the 3/5/6 tricyclic framework were probed into the biomimetic monomer named （+）-chloranthalactone A. Starting from the prepared （R）-Hajos-Wiechert ketone， a trans-fused， thermodynamically unstable hydrindanone was synthesized and further exploration ensured the asymmetric synthesis of congested 3/5/6 core skeleton by way of Wharton transposition and Simmons-Smith reaction. Subsequently， the syntheses of unsaturated lactones were accomplished basing on the strategies of ketone transposition and [2+2] electro-cyclization/ring-opening/lactonization. This work has revealed biogenesis pathway of （+）-chloranthalactone F and to determine its absolute configuration.

Keywords：Total synthesis； sesquiterpenoid； chloranthalactone A； chloranthalactone F

阅读全文链接（需实名注册）：http：//www.nstrs.cn/xiangxiBG.aspx？id=50051&flag=1