Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering , East China Normal University , 3663N Zhongshan Road , Shanghai 200062 , China.
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development , East China Normal University , 3663N Zhongshan Road , Shanghai 200062 , China.
J Am Chem Soc. 2019 Oct 16;141(41):16208-16212. doi: 10.1021/jacs.9b08577. Epub 2019 Oct 3.
The asymmetric total synthesis of (-)-viridin and (-)-viridiol, antifungal metabolites, was achieved in 17 and 18 steps from a commercially available starting material. An intramolecular [3+2] cycloaddition was applied to an easily available -ribose derivative in order to construct the highly substituted D ring containing the key chiral -triol fragment. Co-catalyzed metal-hydride H atom transfer (MHAT) radical cyclization was utilized to form the C-ring and the all-carbon quaternary center at C-10. This convergent strategy provides a scalable approach to prepare viridin and viridiol for biological studies.
(-)- 威碟霉素和 (-)- 威碟醇这两种抗真菌代谢产物的不对称全合成是从一种商业可得的起始原料出发，经 17 步和 18 步反应完成的。我们应用分子内 [3+2] 环加成反应，对一种易得的 -D- 核糖衍生物进行了环化，构建了高度取代的 D 环，其中包含关键的手性 - 三醇片段。我们还采用共催化的金属氢化物氢原子转移（MHAT）自由基环化反应，形成 C 环和 C-10 位的全碳季碳原子。这种收敛性策略为生物研究中制备威碟霉素和威碟醇提供了一种可规模化的方法。
