Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (10): 4021-4027.DOI: 10.6023/cjoc202105059 Previous Articles     Next Articles

ARTICLES

石杉碱甲及其类似物吡啶稠合手性双环[3.3.1]壬烷骨架的不对称构建

宾怀玉, 程立, 杨小会, 谢建华*(), 周其林   

  1. 南开大学化学学院 元素有机化学国家重点实验室 天津 300071
  • 收稿日期:2021-05-31 修回日期:2021-07-07 发布日期:2021-07-19
  • 通讯作者: 谢建华
  • 基金资助:
    国家自然科学基金(21871152); 国家自然科学基金(92056105); 国家自然科学基金(21532003); 国家自然科学基金(21790332)

Enantioselective Construction of the Pyridine-Fused Chiral Bicyclo- [3.3.1]nonane Skeleton of Huperzine A and Its Analogues

Huaiyu Bin, Li Cheng, Xiaohui Yang, Jianhua Xie(), Qilin Zhou   

  1. State Key Laboratory and Institute of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071
  • Received:2021-05-31 Revised:2021-07-07 Published:2021-07-19
  • Contact: Jianhua Xie
  • Supported by:
    National Natural Science Foundation of China(21871152); National Natural Science Foundation of China(92056105); National Natural Science Foundation of China(21532003); National Natural Science Foundation of China(21790332)

A concise strategy for the enantioselective construction of the pyridine-fused chiral bicyclo[3.3.1]nonane skeleton of (+)-huperzine A and its nanlogues was reported. The key features of this strategy are the catalytic asymmetric hydrogenation of an exocyclic γ,δ-unsaturated β-ketoester via dynamic kinetic resolution combined with an intramolecular arylation as the key steps to constuct the pyridine-fused chiral bicyclo[3.3.1]nonane skeleton. This strategy provides a concise and rapid approach to the chiral core structure of huperzine A and its nanlogues from the known starting materials (5 steps and 17.4% overall yield).

Key words: arylation, asymmetric hydrogenation, bicyclo[3.3.1]nonane skeleton, huperzine A, unsaturated ketoester