Insect pheromones and their analogs

XXIII. Synthesis of (7R,8S)-(+)-cis-2-methyl-7,8-epoxyoctadecane — The sex pheromone of Porthetria dispar

Abstract

A four-stage asymmetric synthesis of (+)-disparlure [(7R,8S)-(+)-cis-methyl-7,8-epoxyoctadecane (V)] has been effected from 8-methylnon-2Z-en-l-ol (I), obtained by the carboalumination of acetylene with tris(5-methylhexyl)aluminum using the Sharpless reaction. The asymmetric epoxidation of (I), (Ar, mol. sieve A, (+)-DET, (iOPr)4Ti, t-BuOOH, −15°C, 20 h; H2O, 1 h, NaOH, −7°C, 30 min) gave 8-methyl-2S,3R-epoxynonan-l-ol (II), which was oxidized (kieselguhr-CrO3-Py, 0°C, 2 h; 25°C, 2 h) to 8-methyl-2S,3R-epoxynonan-l-al (III). The coupling of (III) with n-C8H17CH=PPh3 (−78°C, 1 h; 25°C, 15 h) gave 2-methyl-7R,8S-epoxyoctadec-9Z-ene (IV), the hydrogenation (H2/5% Pd-C, 25°C, 5 days) of which led to (V) in admixture with an isomerization product. Compound (V) was isolated by HPLC. Substance, yield, [α] 25D : (II), 73, −2.75°; (III), 80, [80.8°; (IV), 50, +37.25°; (V), 50, +0.8°. The IR and PMR spectra of (II–IV), the13C NMR spectra of (II) and (III), and the mass spectrum of (IV) are given.

This is a preview of subscription content, access via your institution.

Literature cited

  1. 1.

    K. Mori, T. Takigawa, and M. Matsui, Tetrahedron,35, No. 7, 833 (1979).

    CAS  Article  Google Scholar 

  2. 2.

    W. H. Pirkle and P. J. Rinaldi, J. Org. Chem.,44, No. 7, 1025 (1979).

    CAS  Article  Google Scholar 

  3. 3.

    U. M. Dzhemilev, R. N. Fakhretdinov, A. G. Telin, G. A. Tolstikov, and Sr. R. Rafikov, Dokl. Akad. Nauk SSSR,271, No. 2, 361 (1983).

    CAS  Google Scholar 

  4. 4.

    G.-Q. Lin, B.-C. Wu, L.-Y. Liu, X.-Q. Wang, and W.-S. Zhou, Huaxue Xuebao [Acta Chim. Sin.],42, No. 8, 797 (1984).

    CAS  Google Scholar 

  5. 5.

    O. Achmatowicz and A. Sadownik, Carbohydr. Chem.,4, No. 3, 435 (1985).

    CAS  Article  Google Scholar 

  6. 6.

    Y. Masaki, Y. Serizawa, K. Nagata, H. Oda, H. Nagashima, and K. Kaji, Tetrahedron Lett.,27, No. 2, 231 (1986).

    CAS  Article  Google Scholar 

  7. 7.

    V. B. Jigajinni and R. H. Wightman, Carbohydr. Res.,147, No. 1, 145 (1986).

    CAS  Article  Google Scholar 

  8. 8.

    S. Pikul, M. Kozlowska, and J. Jurczak, Tetrahedron Lett.,28, No. 23, 2627 (1987).

    CAS  Article  Google Scholar 

  9. 9.

    A. G. Tolstikov, N. V. Khakhalina, and V. N. Odinolov, Zh. Org. Khim.,23, No. 11, 2469 (1987).

    CAS  Google Scholar 

  10. 10.

    B. E. Rossiter, T. Katsuki, and K. B. Sharpless, J. Am. Chem. Soc.,103, 464 (1981).

    CAS  Article  Google Scholar 

  11. 11.

    K. Mori and T. Ebata, Tetrahedron Lett.,22, No. 43, 4371 (1981).

    Article  Google Scholar 

  12. 12.

    G. Q. Lin, Y.-Y. Jiang, and W.-S. Zhou, Huaxue Xuebao [Acta Chim. Sin.],43, No. 10, 988 (1985).

    CAS  Google Scholar 

  13. 13.

    K. Mori and T. Ebata, Tetrahedron,42, No. 13, 3471 (1986).

    CAS  Article  Google Scholar 

  14. 14.

    Y. D. Prestwich, Science,238, No. 4818, 999 (1987).

    Article  Google Scholar 

  15. 15.

    N. I. Andreeva, A. V. Kuchin, and G. A. Tolstikov, Zh. Obshch. Khim.,55, No. 6, 1316 (1985).

    CAS  Google Scholar 

  16. 16.

    R. M. Hanson and K. B. Sharpless, J. Org. Chem.,51, 1922 (1986).

    CAS  Article  Google Scholar 

  17. 17.

    V. N. Odinokov, V. R. Akhmetova, G. A. Tolstikov, A. M. Moiseenkov, and A. V. Semenovskii, Zh. Org. Khim.,21, No. 3, 489 (1985).

    CAS  Google Scholar 

Download references

Authors

Additional information

Institute of Chemistry, Bashkir Scientific Center, Urals Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 715–718, September–October, 1989.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Odinokov, V.N., Akhmetova, V.R., Khasanov, K.D. et al. Insect pheromones and their analogs. Chem Nat Compd 25, 610–613 (1989). https://doi.org/10.1007/BF00598087

Download citation

Keywords

  • Gossypol
  • Allyl Alcohol
  • Insect Pheromone
  • Epoxyalcohol
  • Asymmetric Epoxidation