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

doi:10.6023/cjoc202107005

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (11): 4437-4443.DOI: 10.6023/cjoc202107005 Previous Articles Next Articles

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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^*()

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()

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)

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Abstract

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

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Gucheng Yuan, Jiawei Liu, Shihang Yu, Chaonan Yuan, Qinghua Bian, Min Wang, Jiangchun Zhong. Asymmetric Synthesis of (3Z,6Z,9S,10R)-9,10-Epoxy-3,6-heneicosadiene, Sex Pheromone Component of Hyphantria cunea[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4437-4443.

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Fig. & Tab. 5

Figure 1. Sex pheromone components of Hyphantria cunea

Scheme 1. Retrosynthetic analysis of sex pheromone 5

Scheme 2. Synthesis of epoxy tosylate 13

Scheme 3. Synthesis of 3,5-dinitrobenzoates rac-9' and (2S,3R)-9'

Scheme 4. Synthesis of sex pheromone 5

References 29

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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

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

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Fig. & Tab. 5

References 29

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