环杷明DEF环螺环核心的合成。
Synthesis of the DEF-Ring Spirocyclic Core of Cyclopamine.
作者信息
Shao Hao, Liu Wenheng, Fang Zhengqi, He Haibing, Gao Shuanhu
机构信息
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China.
Shanghai Frontiers Science Center of Molecule Intelligent Syntheses, School of Chemistry and Molecular Engineering, Wuhu Hospital Affiliated to East China Normal University, East China Normal University, Shanghai, 200062, China.
出版信息
J Org Chem. 2024 Mar 15;89(6):4215-4220. doi: 10.1021/acs.joc.3c02804. Epub 2024 Feb 23.
A stereoselective synthesis of the DEF-ring spirocyclic core of cyclopamine was accomplished using commercially available materials. The key steps in the synthesis were (i) the enantioselective vinylogous Mannich reaction, followed by lactamization to generate the piperidine F ring, and (ii) intramolecular oxidative dearomative spiroetherification to construct the DEF-ring spirocyclic core of cyclopamine. We found that the stereochemistry of the spirocyclization was controlled by the configuration of the methyl group (C-20) in the substrate.
使用市售原料完成了环杷明DEF环螺环核心的立体选择性合成。合成中的关键步骤为：（i）对映选择性乙烯基曼尼希反应，随后进行内酰胺化反应生成哌啶F环；（ii）分子内氧化去芳构化螺醚化反应以构建环杷明的DEF环螺环核心。我们发现螺环化反应的立体化学受底物中甲基（C-20）构型的控制。
Zotero 插件