State Key Laboratory of Bioorganic and Natural Products Chemistry, Collaborative Innovation Center of Chemistry for Life Sciences, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China) http://angligroup.sioc.ac.cn.
Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6878-82. doi: 10.1002/anie.201501021. Epub 2015 Apr 23.
The first total synthesis of mycoleptodiscin A, a structurally unusual indolosesquiterpenoid possessing an ortho-benzoquinone motif, has been accomplished. A sulfone alkylation coupled two readily available fragments to give an aryl triene intermediate. The tetracyclic core of the molecule was assembled through a highly enantioselective iridium-catalyzed polyene cyclization. The benzylic homologation was achieved by a cationic cyanation. The indole motif was constructed via a copper-mediated intramolecular C-N bond formation at a late stage.
首例 mycoleptodiscin A 的全合成已经完成，mycoleptodiscin A 是一种结构特殊的吲哚倍半萜烯，具有邻苯醌结构。通过磺酸酯的烷基化反应，两个易得的片段连接起来形成芳基三烯中间体。通过高度对映选择性的铱催化多烯环化反应构建了四环核心。苄基同系化通过阳离子氰化反应实现。吲哚结构是通过后期铜介导的分子内 C-N 键形成构建的。
