Li Ruoxi, Wu Jingjing
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, No. 429, Zhangheng Road, Shanghai 200213, P. R. China.
Org Lett. 2023 Sep 1;25(34):6278-6283. doi: 10.1021/acs.orglett.3c02076. Epub 2023 Aug 18.
A synthesis of alstoscholarinoid B () and 3-acetoxy-11-hydroxy-11(12 → 13)oleanan-12-al () has been accomplished in 7-9 steps and 10%-16% overall yield from oleanolic acid. This synthesis featured a bioinspired SmI-mediated reductive aldol reaction to establish the -11(12 → 13)-oleanane framework of both and and a -aldol/aldol/lactonization cascade to fully construct the skeleton of . Moreover, the investigation of the bioinspired aldol reaction also sheds light on the potential biogenesis of natural products.
从齐墩果酸出发，经7至9步反应，以10% - 16%的总收率完成了阿尔斯托查洛内酯B（）和3 - 乙酰氧基 - 11 - 羟基 - 11(12→13)齐墩果烷 - 12 - 醛（）的合成。该合成的特点是采用受生物启发的二碘化钐介导的还原羟醛反应来构建和的 - 11(12→13) - 齐墩果烷骨架，以及一个 - 羟醛/羟醛/内酯化串联反应来完全构建的骨架。此外，对受生物启发的羟醛反应的研究也为天然产物的潜在生物合成提供了线索。
