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.
Angew Chem Int Ed Engl. 2022 Apr 11;61(16):e202200576. doi: 10.1002/anie.202200576. Epub 2022 Feb 21.
We have achieved a bioinspired total synthesis of (+)-euphorikanin A, which possesses an intriguing and complex 5/6/7/3-fused tetracyclic skeleton bearing a bridged [3.2.1]-γ-lactone moiety. Key transformations include stereoselective alkylation and aldol condensation to install the main stereocenters, an intramolecular nucleophile-catalyzed aldol lactonization of carboxylic acid-ketone to assemble the five-membered ring, a McMurry coupling to construct the seven-membered ring, and a biomimetic benzilic acid type rearrangement to form the bridged [3.2.1]-γ-lactone moiety.
我们实现了 (+)-euphorikanin A 的仿生全合成，该化合物具有引人入胜的复杂 5/6/7/3-稠合四环骨架，带有桥接的[3.2.1]-γ-内酯部分。关键转化包括立体选择性烷基化和醛醇缩合以安装主要的立体中心，羧酸-酮的分子内亲核催化的醛醇内酯化以组装五元环，McMurry 偶联构建七元环，以及仿生苯并酸型重排形成桥接的[3.2.1]-γ-内酯部分。
