Li Bo, Tan Chuanzhen, Ma Tianhao, Jia Yanxing
State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, and Chemical Biology Center, Peking University, Xue Yuan Rd. 38, Beijing, 100191, China.
Ningbo Institute of Marine Medicine, Peking University, Ningbo, 315010, China.
Angew Chem Int Ed Engl. 2024 Mar 4;63(10):e202319306. doi: 10.1002/anie.202319306. Epub 2024 Jan 24.
We have achieved the first total synthesis of bipolarolides A and B, which possess an intriguing and complex 5/6/6/6/5 caged pentacyclic skeleton with seven contiguous stereocenters. The synthesis features a lithium-halogen exchange/intermolecular nucleophilic addition to link two enantioenriched fragments, two ring-closing metathesis reactions to assemble the five- and eight-membered rings, and a bioinspired Prins reaction/ether formation cascade cyclization to construct the 5/6/6/6/5 caged skeleton.
我们首次完成了双极内酯A和B的全合成，它们具有一个引人入胜且复杂的5/6/6/6/5笼状五环骨架，带有七个相邻的立体中心。该合成方法的特点包括：通过锂-卤交换/分子间亲核加成连接两个对映体富集的片段；通过两个关环复分解反应构建五元环和八元环；以及通过一个受生物启发的普林斯反应/醚形成级联环化反应构建5/6/6/6/5笼状骨架。
