Guo Lian-Dong, Huang Xiong-Zhi, Luo Shi-Peng, Cao Wen-Sen, Ruan Yuan-Ping, Ye Jian-Liang, Huang Pei-Qiang
Department of Chemistry and The Key Laboratory for Chemical Biology of Fujian Province, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian, 361005, P.R. China.
State Key Laboratory of Applied Organic Chemistry Lanzhou University, Lanzhou, 730000, P.R. China.
Angew Chem Int Ed Engl. 2016 Mar 14;55(12):4064-8. doi: 10.1002/anie.201512005. Epub 2016 Feb 17.
The first total synthesis of the alkaloid (-)-haliclonin A is reported. The asymmetric synthesis relied on a novel organocatalytic asymmetric conjugate addition of nitromethane with 3-alkenyl cyclohex-2-enone to set the stereochemistry of the all-carbon quaternary stereogenic center. The synthesis also features a Pd-promoted cyclization to form the 3-azabicyclo[3,3,1]nonane core, a SmI2 -mediated intermolecular reductive coupling of enone with aldehyde to form the requisite secondary chiral alcohol, ring-closing alkene and alkyne metathesis reactions to build the two aza-macrocyclic ring systems, and an unprecedented direct transformation of enol into enone.
报道了生物碱（-）-海克隆宁A的首次全合成。该不对称合成依赖于一种新型有机催化的硝基甲烷与3-烯基环己-2-烯酮的不对称共轭加成反应，以确定全碳季碳手性中心的立体化学。该合成还具有以下特点：通过钯促进的环化反应形成3-氮杂双环[3,3,1]壬烷核心；通过二碘化钐介导的烯酮与醛的分子间还原偶联反应形成所需的二级手性醇；通过闭环烯烃和炔烃复分解反应构建两个氮杂大环环系；以及烯醇到烯酮的前所未有的直接转化反应。
