Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Front End Innovation , LEO Pharma , A/S Industriparken 55 , 2750 Ballerup , Denmark.
J Am Chem Soc. 2018 Jun 20;140(24):7462-7465. doi: 10.1021/jacs.8b04891. Epub 2018 Jun 11.
A divergent strategy for assembling pyrone diterpenes is presented. Capitalizing on the unique stereo- and chemoselectivity features of radical-based chemistry, the core decalin of these structures is efficiently forged using an electrochemically assisted oxidative radical polycyclization while key peripheral substituents are appended using decarboxylative radical cross couplings. In this way, access to four natural products (subglutinols A/B, higginsianin A, and sesquicillin A) is achieved in a concise and stereocontrolled fashion that is modular and amenable to future medicinal chemistry explorations.
呈现了一种用于组装吡喃二萜的发散策略。利用基于自由基化学的独特立体选择性和化学选择性特征，通过电化学辅助氧化自由基多环化反应高效构建这些结构的核心十氢萘环，同时使用脱羧基自由基交叉偶联反应添加关键的外围取代基。通过这种方式，以简洁、立体控制的方式获得了四个天然产物（subglutinols A/B、higginsianin A 和 sesquicillin A），这种方式具有模块化特征，并且适合未来的药物化学探索。
