高等学校化学学报

高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (12): 2676.doi: 10.7503/cjcu20120494

• 有机化学 • 上一篇    下一篇

氧吲哚生物碱Humantenine关键骨架的立体选择性构建

肖涛, 周旋, 宋颢   

  1. 四川大学华西药学院, 成都 610041
  • 收稿日期:2012-05-23 出版日期:2012-12-10 发布日期:2012-11-20
  • 通讯作者: 周旋,男,博士,主要从事天然产物全合成研究.E-mail:zhouxuan526@gmail.com宋颢,女,博士,讲师,主要从事天然产物全合成研究.E-mail:songhao@scu.edu.cn E-mail:zhouxuan526@gmail.com;songhao@scu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号: 21021001)资助.

Stereoselective Construction of the Key Skeleton of Oxindole Alkaloid Humantenine

XIAO Tao, ZHOU Xuan, SONG Hao   

  1. West China School of Pharmacy, Sichuan University, Chengdu 610041, China
  • Received:2012-05-23 Online:2012-12-10 Published:2012-11-20

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摘要：

通过炔锂试剂11与环氮化合物10的区域和立体选择性加成构建了humantenine等钩吻生物碱不对称全合成路线中的重要中间体13; 通过酸催化的烯醇-氧环合策略一步构建了humantenine等钩吻生物碱结构中的四氢吡喃环、 环氧己烷、 C7季碳中心和C3手性中心; 最终从已知化合物7出发, 以16步1.5%的总收率完成了humantenine(2), humantenine N4-oxide(3), gelseganines A(4)和gelseganines B(5)等钩吻生物碱关键中间体化合物6的不对称合成.

关键词: Humantenine, 不对称合成, 烯醇-氧环合, 氧吲哚生物碱

Abstract:

Humantenine-type compounds are a group of Gelsemium alkaloids isolated from Gelsemium elegans Benth that possess complex structures and remarkable activities. In this work, the synthetic approaches of them were investigated. The key structure of Gelsemium alkaloids humantenine(13) was efficiently constructed through a region- and stereoselectivity addition of compound 11 to compound 10. A multi-step, one pot eno-loxonium cyclization cascade was used in a highly efficient way to construct, simultaneously, the tetrahydropyran ring, oxepane ring, C3 chiral carbon and C7 chiral quaternary carbon of humantenine(2). Based the above created methodology, the key skeleton(6) of oxindole alkaloid humantenine(2), humantenine N4-oxide(3), gelseganines A(4)and gelseganines B(5) was asymmetric synthesized in 16 steps with a total yield of 1.5%. The structures of the compounds were confirmed by IR, 1H NMR, 13C NMR and high resolution mass spectrometer(HRMS). Especially, we successfully synthesized hmantenine-type skeleton which indicates this method has a widely range of applications.

Key words: Humantenine, Asymmetric synthesis, Enol-oxonium cyclization, Oxindole alkaloid

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