有机化学 ›› 2021, Vol. 41 ›› Issue (11): 4437-4443.DOI: 10.6023/cjoc202107005 上一篇    下一篇

研究论文

美国白蛾性信息素(3Z,6Z,9S,10R)-9,10-环氧-3,6-二十一碳二烯的不对称合成

袁谷城, 刘嘉威, 于士航, 原超楠, 边庆花, 王敏, 钟江春*()   

  1. 中国农业大学理学院 应用化学系 北京 100193
  • 收稿日期:2021-07-02 修回日期:2021-07-17 发布日期:2021-08-09
  • 通讯作者: 钟江春
  • 作者简介:
    † 共同第一作者.
  • 基金资助:
    国家重点研发计划(2017YFD0201404)

Asymmetric Synthesis of (3Z,6Z,9S,10R)-9,10-Epoxy-3,6-heneicosadiene, Sex Pheromone Component of Hyphantria cunea

Gucheng Yuan, Jiawei Liu, Shihang Yu, Chaonan Yuan, Qinghua Bian, Min Wang, Jiangchun Zhong()   

  1. College of Science, China Agricultural University, Beijing 100193
  • Received:2021-07-02 Revised:2021-07-17 Published:2021-08-09
  • Contact: Jiangchun Zhong
  • About author:
    † These authors contributed equally to this work.
  • Supported by:
    National Key Research and Development Program of China(2017YFD0201404)

美国白蛾是一种严重危害农、林业的世界性检疫害虫, 其性信息素的主要活性成分为(3Z,6Z,9S,10R)-9,10-环氧- 3,6-二十一碳二烯. 以1-溴十一烷为起始原料, 经卤代烃的亲核取代、醋酸镍/硼氢化钠催化氢化、Sharpless不对称环氧化、高氯酸开环、烷基环氧重排(包括环氧开环与碳酸钾催化关环)等11步反应, 总收率为14%, 发展了一种新的合成美国白蛾性信息素主要活性成分的方法.

关键词: 美国白蛾, 信息素合成, Sharpless不对称环氧化, 烷基环氧重排

Hyphantria cunea is an important worldwide pest due to its destructiveness to the crops and trees. The main active component of its sex pheromone is (3Z,6Z,9S,10R)-9,10-epoxy-3,6-henicosadiene. A new synthesis of the sex pheromone from 1-bromoundecane was developed. The procedure includes 11 steps, and the overall yield is 14%. Furthermore, nucleophilic substitution of alkyl halide, partial hydrogenation with nickel boride, Sharpless asymmetric epoxidation, ring opening with HClO4, and alkylative epoxide rearrangement (invovling the ring opening of terminal epoxide and the ring-closure with K2CO3) are crucial steps.

Key words: Hyphantria cunea, synthesis of pheromone, Sharpless asymmetric epoxidation, alkylative epoxide rearrangement