Citation: Sun Zhi-Feng, Zhou Lu-Nan, Zhang Tao, Du Zhen-Ting. Stereoselective synthesis of the Paulownia bagworm sex pheromone[J]. Chinese Chemical Letters, ;2017, 28(3): 558-562. doi: 10.1016/j.cclet.2016.11.018 shu

Stereoselective synthesis of the Paulownia bagworm sex pheromone

Sun Zhi-Feng ^a,b ,
Zhou Lu-Nan ^a ,
Zhang Tao ^a,, ,
Du Zhen-Ting ^a,,

a.
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Science, Northwest A & F University, Yangling 712100, China
b.
College of Chemical and Environment Science, Shaanxi University of Technology, Hanzhong, 723001, China

Corresponding author: Zhang Tao, fuzitong@163.com Du Zhen-Ting, duzt@nwsuaf.edu.cn
Received Date: 17 August 2016
Revised Date: 28 October 2016
Accepted Date: 1 November 2016
Available Online: 18 March 2016

Figures(4)

According to our retrosynthesis, the main chain of the target molecule could be constructed using a C5+C7+C5 strategy. The key induction reaction afforded chiral methyl group moieties using different Evans templates with different configurations. Li₂CuCl₄ was effectively employed in the Csp³-Csp³ coupling protocol. The target molecular was obtained in a 12.6% overall yield with nine steps in the longest linear route.
- Pheromone,
- Paulownia bagworm,
- Evans template,
- Total synthesis
1. [1]
  (a) P. Trematerra, Advances in the use of pheromones for stored-product protection, J. Pest Sci. 85(2012) 285-299;
  (b) M.A.Silva, G.C.D. Bezerra-Silva, T. Mastrangelo, The host marking pheromone application on the management of fruit flies-a review, Braz. Arch. Biol. Technol. 55(2012) 835-842.
2. [2]
  Cui G.Z., Zhu J.J.. Pheromone-based pest management in China:past, present, and future prospects[J]. J. Chem. Ecol., 2016,42:557-570. doi: 10.1007/s10886-016-0731-x
3. [3]
  (a) C. Che, Z.N. Zhang, A facile synthetic method for (3Z 6Z, 9S, 10R)-9, 10-epoxy-3, 6-heneicosadiene, sex pheromone component of Hyphantria cunea (drug), Chin. Chem. Lett. 16(2005) 468-470;
  (b) B. Sun, L.Z. Peng, X.S. Chen, Y.L. Li, Y. Li, Short and stereoselective synthesis of the (-)-(5R 6S)-6-acetoxyhexadecane-5-olide, Chin. Chem. Lett. 15(2004) 1177-1178.
4. [4]
  Gries R., Khaskin G., Tan Z.X.. (1S)-1-Ethyl-2-methylpropyl 3, 13-dimethylpentadecanoate:major sex pheromone component of Paulownia bagworm Clania variegata[J]. J. Chem. Ecol., 2006,32:1673-1685. doi: 10.1007/s10886-006-9101-4
5. [5]
  Zhao B.G., El-Sayed A.M., Wang S.F.. Determination of the sex hormone 3-D configuration from the Clania variegata by field trapping[J]. China Forest. Sci. Technol., 2009,23:21-22.
6. [6]
  (a) K. Mori, T. Tashiro, B. Zhao, D.M. Suckling, A.M. El-Sayed, Pheromone synthesis. Part 243:synthesis and biological evaluation of (3R, 13R, 1'S)-1'-ethyl-2'-methylpropyl 3, 13-dimethyl pentadecanoate, the major component of the sex pheromone of Paulownia bagworm, Clania variegata, and its stereoisomers, Tetrahedron 66(2010) 2642-2653;
  (b) T. Taguri, M. Yamamoto, T. Fujii, Y. Muraki, T. Ando, Synthesis of four stereoisomers of (S)-2-methylpent-3-yl 3, 13-dimethylpentadecanoate, a sex pheromone of the bagworm moth Clania variegate, using stereospecific inversion of secondary sulfonates as a key step, Eur. J. Org. Chem. (2013) 6924-6933.
7. [7]
  (a) T. Zhang, J. Feng, C. Cai, X. Zhang, Synthesis and field test of three candidates for Soybean Pod Borer's sex pheromone, Nat. Prod. Commun. 9(2011) 1323-1326;
  (b) T. Zhang, W.L. Ma, T.R. Li, et al., A facile asymmetric synthesis of (S)-14-methyl-1-octadecene, the sex pheromone of the peach leafminer moth, Molecules 18(2013) 5201-5208.
8. [8]
  (a) D.A. Evans, M.D. Ennis, D.J. Mathre, Asymmetric alkylation reactions of chiral imide enolates. A practical approach to the enantioselective synthesis of α-substituted carboxylic acid derivatives, J. Am. Chem. Soc. 104(1982) 1737-1739;
  (b) J.S. Yadav, N.N. Yadav, T.S. Rao, B.V.S. Reddy, A.A.K.A. Ghamdi, Enantioselective total synthesis of (+)-vittatalactone, Eur. J. Org. Chem. (2011) 4603-4608.
9. [9]
  Organ M.G., Bilokin Y.V., Bratovanov S.. Approach toward the total synthesis of orevactaene:convergent and stereoselective synthesis of the C18-C31 domain of orevactaene. Evidence for the relative configuration of the side chain[J]. J. Org. Chem., 2002,67:5176-5183. doi: 10.1021/jo0201777
10. [10]
  (a) S. Shan, Y. Jun, Studies on insect pheromones. I. Stereoselective synthesis of the sex pheromone of Khapra beetle, (Z)-14-methyl-8-hexadecenal, Acta Chim. Sinica 46(1988) 1045-1048;
  (b) E.G. Neeland, J.P. Ounsworth, R.J. Sims, L. Weiler, Synthesis, conformational analysis, and stereoselective reduction of 14-membered ring 3-keto lactones, J. Org. Chem. 59(1994) 7383-7394.
1. [1]
  Tengfei Xuan , Xinyu Zhang , Wei Han , Yidong Huang , Weiwu Ren . Total synthesis of (+)-taberdicatine B and (+)-tabernabovine B. Chinese Chemical Letters, 2025, 36(2): 109816-. doi: 10.1016/j.cclet.2024.109816
2. [2]
  Jingping Hu , Jing Xu . Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C₁₄–epi-deoxycalyciphylline H. Chinese Chemical Letters, 2024, 35(4): 108733-. doi: 10.1016/j.cclet.2023.108733
3. [3]
  Zhenhao Wang , Yuliang Tang , Ruyu Li , Shuai Tian , Yu Tang , Dehai Li . Bioinspired synthesis of cochlearol B and ganocin A. Chinese Chemical Letters, 2024, 35(7): 109247-. doi: 10.1016/j.cclet.2023.109247
4. [4]
  Peng Chen , Lijuan Liang , Yufei Zhu , Zhimin Xing , Zhenhua Jia , Teck-Peng Loh . Strategies for constructing seven-membered rings: Applications in natural product synthesis. Chinese Chemical Letters, 2024, 35(6): 109229-. doi: 10.1016/j.cclet.2023.109229
5. [5]
  Peng Zhou , Ziang Jiang , Yang Li , Peng Xiao , Feixiang Wu . Sulphur-template method for facile manufacturing porous silicon electrodes with enhanced electrochemical performance. Chinese Chemical Letters, 2024, 35(8): 109467-. doi: 10.1016/j.cclet.2023.109467
6. [6]
  Pengfei Zhang , Qingxue Ma , Zhiwei Jiang , Xiaohua Xu , Zhong Jin . Transition-metal-catalyzed remote meta-C—H alkylation and alkynylation of aryl sulfonic acids enabled by an indolyl template. Chinese Chemical Letters, 2024, 35(8): 109361-. doi: 10.1016/j.cclet.2023.109361
7. [7]
  Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO₃₋_x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
8. [8]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
9. [9]
  Huimin Luan , Qinming Wu , Jianping Wu , Xiangju Meng , Feng-Shou Xiao . Templates for the synthesis of zeolites. Chinese Journal of Structural Chemistry, 2024, 43(4): 100252-100252. doi: 10.1016/j.cjsc.2024.100252
10. [10]
  Zhaojun Liu , Zerui Mu , Chuanbo Gao . Alloy nanocrystals: Synthesis paradigms and implications. Chinese Journal of Structural Chemistry, 2023, 42(11): 100156-100156. doi: 10.1016/j.cjsc.2023.100156
11. [11]
  Hui Jin , Qin Cai , Peiwen Liu , Yan Chen , Derong Wang , Weiping Zhu , Yufang Xu , Xuhong Qian . Multistep continuous flow synthesis of Erlotinib. Chinese Chemical Letters, 2024, 35(4): 108721-. doi: 10.1016/j.cclet.2023.108721
12. [12]
  Caihong Mao , Yanfeng He , Xiaohan Wang , Yan Cai , Xiaobo Hu . Synthesis and molecular recognition characteristics of a tetrapodal benzene cage. Chinese Chemical Letters, 2024, 35(8): 109362-. doi: 10.1016/j.cclet.2023.109362
13. [13]
  Mei Peng , Wei-Min He . Photochemical synthesis and group transfer reactions of azoxy compounds. Chinese Chemical Letters, 2024, 35(8): 109899-. doi: 10.1016/j.cclet.2024.109899
14. [14]
  Liyong Ding , Zhenhua Pan , Qian Wang . 2D photocatalysts for hydrogen peroxide synthesis. Chinese Chemical Letters, 2024, 35(12): 110125-. doi: 10.1016/j.cclet.2024.110125
15. [15]
  Xiaoyu Chen , Jiahao Hu , Jingyi Lin , Haiyang Huang , Changqing Ye , Hongli Bao . Biisoindolylidene solvatochromic fluorophores: Synthesis and photophysical properties. Chinese Chemical Letters, 2025, 36(2): 109923-. doi: 10.1016/j.cclet.2024.109923
16. [16]
  Yuqing Liu , Yu Yang , Yuhan E , Changlong Pang , Di Cui , Ang Li . Insight into microbial synthesis of metal nanomaterials and their environmental applications: Exploration for enhanced controllable synthesis. Chinese Chemical Letters, 2024, 35(11): 109651-. doi: 10.1016/j.cclet.2024.109651
17. [17]
  Wenyi Mei , Lijuan Xie , Xiaodong Zhang , Cunjian Shi , Fengzhi Wang , Qiqi Fu , Zhenjiang Zhao , Honglin Li , Yufang Xu , Zhuo Chen . Design, synthesis and biological evaluation of fluorescent derivatives of ursolic acid in living cells. Chinese Chemical Letters, 2024, 35(5): 108825-. doi: 10.1016/j.cclet.2023.108825
18. [18]
  Shengkai Li , Yuqin Zou , Chen Chen , Shuangyin Wang , Zhao-Qing Liu . Defect engineered electrocatalysts for C–N coupling reactions toward urea synthesis. Chinese Chemical Letters, 2024, 35(8): 109147-. doi: 10.1016/j.cclet.2023.109147
19. [19]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
20. [20]
  Kebo Xie , Qian Zhang , Fei Ye , Jungui Dai . A multi-enzymatic cascade reaction for the synthesis of bioactive C-oligosaccharides. Chinese Chemical Letters, 2024, 35(6): 109028-. doi: 10.1016/j.cclet.2023.109028

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(686)
HTML views(39)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142