通过晚期骨架重排实现倍半萜的发散性全合成。
Divergent Total Syntheses of Sesquiterpenes through Late-Stage Skeletal Reorganization.
机构信息
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory of Chemical Biology of Fujian Province, iCHEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
出版信息
J Am Chem Soc. 2023 Aug 23;145(33):18642-18648. doi: 10.1021/jacs.3c06442. Epub 2023 Aug 10.
We disclose unified, protecting-group-free, bioinspired divergent total syntheses of eight -cedrane and -prezizaane sesquiterpenes and formal syntheses of five anislactone sesquiterpenes. The efficiency of our approach derives from rapid access to the 15-carbon tricyclic carboxylic acid through cationic epoxide-ene cyclization and HAT oxygenation, transformation of this intermediate into three distinct tricyclic precursors via Lewis acid-mediated skeletal reorganizations, subsequent programmed oxidation level enhancement, and a biomimetic oxidation-initiated skeletal rearrangement cascade. Consequently, we created a synthetic correlation map of the three most prevalent sesquiterpene families.
我们公开了统一的、无保护基团的、受生物启发的分歧全合成方法，用于合成八种 -cedrane 和 -prezizaane 倍半萜以及五种 anislactone 倍半萜的正式合成方法。我们的方法的效率源于通过阳离子环氧化物-烯环化和 HAT 氧化作用快速获得 15 碳三环羧酸，通过路易斯酸介导的骨架重排将该中间体转化为三个不同的三环前体，随后进行程序化的氧化水平增强和仿生氧化引发的骨架重排级联反应。因此，我们创建了三个最常见的倍半萜家族的合成相关图谱。
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