以京尼平为原料的一些萜类天然产物的合成研究

In this project, we plan to synthesize some terpene natural products by using inexpensive and conveniently avaliable geninpin as the starting material. These target molecules including marine natural products Plumisclerin A and Xenicin that possess potent antitumor activity, Prismatomerin, Plumericin, Plumieride and Gaetneroside that have an interesting spiro-ring system. Our studies not only deliver highly efficient routes for assembling these natural products, but also provide new strategy for C-C bond formation, as well as new analogues of these products for further exploring their structure-activity relationship.

在本项目中我们计划以价廉易得的天然产物Genipin作为起始原料，探索对于复杂天然产物如海洋二萜Plumisclerin A，齐尼卡烷（xenicane）骨架的天然产物Xenicin，环烯醚萜类天然产物Prismatomerin, Plumericin, Plumieride和Gaetneroside等的高效合成。我们的研究不仅可以促进这些化合物的全合成，同时也可以发展出新的碳-碳键形成策略等方法。同时这些工作也可以促进对于这些具有重要生理活性天然产物进行相关的结构-活性关系研究。

本项目采用经济易得的京尼平为起始原料，发展了简洁的路线来构建海洋二萜Plumisclerin A的四环骨架和环烯醚萜类 Prismatomerin的螺环结构。从京尼平出发，通过一个高选择性的分子间Diels-Alder反应完成了Plumisclerin A的A/B/C三环构建，随后连续四步立体选择性的环氧化反应、Dauben氧化重排反应引入设计的烯酮片段，最后再通过一个SmI2介导的还原偶联反应完成Plumisclerin A的四环骨架。环烯醚萜类 Prismatomerin的螺环结构则通过一个关键的分子内Baylis-Hillman来构建。进一步的研究仍在进行。