State Key Laboratory of Bioorganic and Natural Products Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
J Am Chem Soc. 2012 May 16;134(19):8078-81. doi: 10.1021/ja302765m. Epub 2012 May 2.
A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6π-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.
已开发出一种用于吲哚萜烯类化合物 anominine（1）及其天然同系物tubingensin A（2）的全合成的发散策略。首先通过 Ueno-Stork 自由基环化和 Sc(OTf)（3）介导的 Mukaiyama 醛醇反应，以立体控制的方式形成关键的 C-C 键，组装具有所有所需手性中心的共同中间体 11。anominine 的路线采用自由基脱氧，然后进行有效的侧链安装，而tubingensin A 的途径则利用 CuOTf 促进的 6π-电环化/芳构化序列来构建五环支架的中心区域。
