Pheromones: synthesis and bioactivity

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Kenji Mori


Abstract

Pheromones play an important role in chemical communication among organisms. Various chiral and non-racemic pheromones have been identified since the late 1960s. Their enantioselective syntheses were achieved so as to establish the absolute configuration of the naturally occurring pheromones and also to clarify the relationship between absolute configuration and the bioactivity of the chiral pheromones. Four recent examples of pheromone synthesis are given. The enantiomers of sordidin 14, the banana weevil pheromone, have been synthesized starting from (S)-propylene oxide. (-)-exo-Isobrevicomin 17 and its (-)-endo-isomer 21, the components of the volatiles of the mountain pine beetle, have been synthesized by employing the Sharpless asymmetric dihydroxylation and lipase-catalysed acetylation as the key reactions. The enantiomers of (Z)-hexadeca-7,15-dien-4-olide 24, the sex pheromone of the yellowish elongate chafer, have been synthesized via lipase-catalysed resolution. Lurlene 27, the pheromone of the green flagellate Chlamydomonas allensworthii, has been synthesized by employing a phenyl sulfone coupling reaction as the key reaction. The relationships between absolute configuration and bioactivity are diverse. For example, neither the (R)- nor the (S)-enantiomer of sulcatol 10, the aggregation pheromone of the ambrosia beetle Gnathotrichus sulcatus, is bioactive, but when combined to give an enantiomeric mixture they become active. In the case of olean 46, the olive fruit fly pheromone, (R)-46 is active for the males, while (S)-46 is active for the females.


References

  1. K. Mori, Tetrahedron Lett., 1973, 3869 CrossRef CAS.
  2. K. Mori, Tetrahedron, 1974, 30, 3817 CrossRef CAS.
  3. R. G. Riley, R. M. Silverstein and J. C. Moser, Science, 1974, 183, 760 CAS.
  4. S. Iwaki, S. Marumo, T. Saito, M. Yamada and K. Katagiri, J. Am. Chem. Soc., 1974, 96, 7842 CrossRef CAS.
  5. K. Mori, Tetrahedron, 1974, 30, 4223 CrossRef CAS.
  6. D. L. Wood, L. E. Browne, B. Ewing, K. Lindahl, W. D. Bedard, P. E. Tilden, K. Mori, G. B. Pitman and P. R. Hughes, Science, 1976, 192, 896 CAS.
  7. S. Kuwahara and K. Mori, Tetrahedron, 1990, 46, 8083 CrossRef CAS.
  8. K. Mori and N. P. Argade, Liebigs Ann. Chem., 1994, 695 Search PubMed.
  9. K. Mori and T. Ebata, Tetrahedron, 1986, 42, 4413 CrossRef CAS.
  10. E. L. Plummer, T. E. Stewart, K. Byrne, G. T. Pearce and R. M. Silverstein, J. Chem. Ecol., 1976, 2, 307 Search PubMed.
  11. K. Mori, in Methods in Chemical Ecology, ed. J. Millar and K. Haynes, Chapman and Hall, New York, 1996, in the press Search PubMed.
  12. W. A. König, Gas Chromatographic Enantiomer Separation with Modified Cyclodextrins, Hüthig, Heidelberg, 1992 Search PubMed.
  13. K. Mori, in The Total Synthesis of Natural Products, ed. J. W. ApSimon, John Wiley, New York, 1981, vol. 4, pp. 1–183 Search PubMed.
  14. K. Mori, in The Total Synthesis of Natural Products, ed. J. W. ApSimon, John Wiley, New York, 1992, vol. 9, pp. 1–534 Search PubMed.
  15. K. Mori, Tetrahedron, 1989, 45, 3233 CrossRef CAS.
  16. K. Mori, in Advances in Asymmetric Synthesis, ed. A. Hassner, JAI Press, Greenwich, 1995, vol. 1, pp. 211–269 Search PubMed.
  17. J. Beauharire, P.-H. Ducrot, C. Malosse, D. Rochat, J. O. Ndiege and D. O. Otiens, Tetrahedron Lett., 1995, 36, 1043 CrossRef.
  18. K. Mori, T. Nakayama and H. Takikawa, Tetrahedron Lett., 1996, 37, 3741 CrossRef CAS.
  19. W. Francke, F. Schröder, P. Philipp, H. Meyer, V. Sinnwell and G. Gries, Bioorg. Med. Chem., 1996, 4, 363 CrossRef CAS.
  20. K. Mori, H. Takikawa, Y. Nishimura and H. Horikiri, Liebigs Ann., 1997, 327 Search PubMed.
  21. W. S. Leal, S. Kuwahara, M. Ono and S. Kubota, Bioorg. Med. Chem., 1996, 4, 315 CrossRef CAS.
  22. T. Nakayama and K. Mori, Liebigs Ann., in the press Search PubMed.
  23. K. Mori, Synlett, 1995, 1097 CrossRef CAS.
  24. R. C. Starr, F.-J. Marner and L. Jaenicke, Proc. Natl. Acad. Sci. USA, 1995, 92, 641 CAS.
  25. L. Jaenicke and F.-J. Marner, Liebigs Ann., 1995, 1343 CAS.
  26. K. Mori and S. Takanashi, Tetrahedron Lett., 1996, 37, 1821 CrossRef CAS.
  27. K. Mori and S. Takanashi, Proc. Jpn. Acad. Ser. B., 1996, 72, 174 Search PubMed.
  28. M. Mohri, H. Kinoshita, K. Inomata and H. Kotake, Chem. Lett., 1985, 451 CAS.
  29. M. Kobayashi, T. Koyama, K. Ogura, S. Seto, F. J. Ritter and J. E. M. Brüggemann-Rotgans, J. Am. Chem. Soc., 1980, 102, 6602 CrossRef CAS.
  30. J. P. Vité, D. Klimetzek, G. Loskant, R. Hedden and K. Mori, Naturwissenschaften, 1976, 63, 582 CrossRef CAS.
  31. J. H. Tumlinson, M. G. Klein, R. E. Doolittle, T. L. Ladd and A. T. Proveaux, Science, 1977, 197, 789 CAS.
  32. M. Mori, K. Mochizuki, M. Kohno, T. Chuman, A. Ohnishi, H. Watanabe and K. Mori, J. Chem. Ecol., 1986, 12, 83 Search PubMed.
  33. H. Kodama, K. Mochizuki, M. Kohno, A. Ohnishi and Y. Kuwahara, J. Chem. Ecol., 1987, 13, 1859 Search PubMed.
  34. R. Nishida and H. Fukami, Mem. Coll. Agric. Kyoto Univ., 1983, 122, 1 Search PubMed.
  35. D. G. James and K. Mori, J. Chem. Ecol., 1995, 21, 403 Search PubMed.
  36. B. S. Lindgren, G. Gries, H. D. Pierce, Jr. and K. Mori, J. Chem. Ecol., 1992, 18, 1201 Search PubMed.
  37. T. L. Payne, J. V. Richerson, J. C. Dickens, J. R. West, K. Mori, C. W. Berisford, R. L. Hedden, J. P. Vité and M. S. Blum, J. Chem. Ecol., 1982, 8, 873 Search PubMed.
  38. J. P. Vité, G. Ohloff and R. F. Billings, Nature, 1978, 272, 817.
  39. S. J. Seybold, T. Ohtsuka, D. L. Wood and I. Kubo, J. Chem. Ecol., 1995, 21, 995 Search PubMed.
  40. G. Szöcs, M. Tóth, W. Francke, F. Schmidt, P. Philipp, W. A. König, K. Mori, B. S. Hansson and C. Löfstedt, J. Chem. Ecol., 1993, 19, 2721 Search PubMed.
  41. J. H. Borden, L. Chong, J. A. McLean, K. N. Slessor and K. Mori, Science, 1976, 192, 894 CAS.
  42. M.-C. Cammaerts and K. Mori, Physiol. Entomol., 1987, 12, 381 CAS.
  43. T. Suzuki, J. Kozaki, R. Sugawara and K. Mori, Appl. Entomol. Zool., 1984, 19, 15 Search PubMed.
  44. G. Haniotakis, W. Francke, K. Mori, H. Redlich and V. Schurig, J. Chem. Ecol., 1986, 12, 1559 Search PubMed.
  45. P. G. McDowell, A. Hassanali and R. Dransfield, Physiol. Entomol., 1985, 10, 183 CAS.
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