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有机化学
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有机化学 ›› 2013, Vol. 33 ›› Issue (12): 2515-2519.DOI: 10.6023/cjoc201308005 上一篇    下一篇

研究论文

(－)-Frontalin的形式合成

周航a, 孙默然a, 曹其伟a, 朱明b, 白磊阳a, 谢阳腊a, 杨华a   

  1. a 郑州大学药学院 郑州 450001;
    b 海口市疾病预防控制中心 海口 571000
  • 收稿日期:2013-08-05 修回日期:2013-09-21 发布日期:2013-09-25
  • 通讯作者: 杨华 E-mail:yanghua@zzu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 21372205)及郑州大学研究生科学研究(No. 12Y03303)资助项目.

Formal Synthesis of (－)-Frontalin

Zhou Hanga, Sun Morana, Cao Qiweia, Zhu Mingb, Bai Leiyanga, Xie Yanglaa, Yang Huaa   

  1. a School of Pharmaceutical Science, Zhengzhou University, Zhengzhou 450001;
    b Haikou Center for Disease Control and Prevention, Haikou 571000
  • Received:2013-08-05 Revised:2013-09-21 Published:2013-09-25
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21372205) and the Graduate Research Project of Zhengzhou University (No. 2Y03303).

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(－)-Frontalin是用于手性叔醇构筑测试的基准分子之一. 以本实验室发展的[2，3]-Meisenheimer重排为关键反应，以L-天冬氨酸衍生物为起始原料，经Wittig反应、酯基还原、二醇双乙酰化、[2，3]-Meisenheimer重排等7步反应，实现了(－)-Frontalin关键中间体的合成，总收率为34%，ee值为94%. 论文工作将[2，3]-Meisenheimer 重排构筑手性叔醇的底物范围，从α，β-不饱和酯基的共轭烯烃扩展至孤立烯烃，充分证明了用[2，3]-Meisenheimer 重排构筑手性叔醇更加一般的特征.

关键词: (－)-Frontalin , 手性叔醇, [2,3]-Meisenheimer重排, Wittig反应

(－)-Frontalin is usually used as one of standard molecules to test the usefulness of chiral tertiary alcohol construction. Based on methodology of chiral tertiary alcohols construction via [2,3]-Meisenheimer rearrangement which has been developing on our laboratory, the formal synthesis of (－)-frontalin is finished via successive Wittig reaction, ester reduction, [2,3]-Meisenheimer rearrangement, and etc. The total yield is 34% and the ee value is 94%. The substrate scope is expanded from α,β-conjugated olefins into isolated olefins. This proves the more general characteristic of chiral tertiary alcohol construction via [2,3]-Meisenheimer rearrangement.

Key words: (－)-frontalin, chiral tertiary alcohol, [2,3]-Meisenheimer rearrangement, Wittig reaction