Understanding host-selective phytotoxicity: Synthesis and biological discrimination of phomalide and its (Z)-isomer

Journal of Organic Chemistry

Volumn 61, Issue 23, 1996, Pages 8008-8009

  Ward, Dale E ^a   Vazquez, Alfredo ^a   Pedras, M Soledade C ^a  

^a UNIVERSITY OF SASKATCHEWAN   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0006386142     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961661a     Document Type: Article

References (38)

1. For a recent multiauthor review on phytotoxins, see: Graniti, A.; et al. Experientia 1991, 47, 751-826.
2. (a) For a recent review on the history and control of blackleg disease, see: Gugel, R. K.; Petrie, G. A. Can. J. Plant Pathol. 1992, 14, 36-45.
3. (b) Canola refers to varieties of rapeseed containing very low amounts of erucic adic and glucosinolates.
4. Pedras, M. S. C.; Taylor, J. T.; Nakashima, T. T. J. Org. Chem. 1993, 58, 4778-4780.
5. For a recent review on phytotoxins of the blackleg fungus, see: Pedras, M. S. C. Rev. Latinoam. Quim. In press.
6. (a) Turner, W. B.; Aldrige, D. C. Fungal Metabolites II; Academic Press: New York, 1983; pp 436-442.
7. (b) Kleinkauf, H.; von Doheren, H. Eur. J. Biochem. 1990, 192, 1-15.
8. (a) Bodanszky, M. Principles of Peptide Synthesis, 2nd ed.; Springer-Verlag: Berlin, 1993.
9. (b) Izumiya, N.; Kato, T.; Aoyagi, H.; Waki, M.; Kondo, M. Synthetic Aspects of Biologically Acitve Cyclic Peptides; Halsted Press: New York, 1979.
10. (c) Kopple, K. D. J. Pharm. Sci. 1972, 61, 1345-1356.
11. Reviews: (a) Schmidt, U.; Lieberknecht, A.; Wild, J. Synthesis 1988, 159-172. (b) Noda, K.; Shimohigashi, Y.; Izumiya, N. In The Peptides; Gross, E.; Meienhofer, J., Eds.; Academic Press: New York, 1983, Vol. 5, pp 285-339.
12. Reviews: (a) Schmidt, U.; Lieberknecht, A.; Wild, J. Synthesis 1988, 159-172. (b) Noda, K.; Shimohigashi, Y.; Izumiya, N. In The Peptides; Gross, E.; Meienhofer, J., Eds.; Academic Press: New York, 1983, Vol. 5, pp 285-339.
13. 7 The (E)-isomers can be prepared by syn-elimination of certain threonine derivatives [(a) Rich, D. H.; Tam, J. P. J. Org. Chem. 1977, 42, 3815-3820] or by anti-elimination of allo-threonine derivatives: (b) Somekh, L.; Shanzer, A. Ibid. 1983, 48, 907-908 and cited references.
14. 7 The (E)-isomers can be prepared by syn-elimination of certain threonine derivatives [(a) Rich, D. H.; Tam, J. P. J. Org. Chem. 1977, 42, 3815-3820] or by anti-elimination of allo-threonine derivatives: (b) Somekh, L.; Shanzer, A. Ibid. 1983, 48, 907-908 and cited references.
15. For a recent example involving (Z)-Aba, see: Li, K. W.; Wu, J.; Xing, W.; Simon, J. A. J. Am. Chem. Soc. 1996, 118, 7237-7238.
16. (a) Cavelier-Frontin, F.; Achmad, S.; Verducci, J.; Jacquier, J.; Pèpe, G. J. Mol. Struct. (THEOCHEM) 1993, 286, 125-130.
17. (b) Ueda, K.; Waki, M.; Izumiya, N. Int. J. Pept. Protein Res. 1987, 30, 33-39 and cited references.
18. 6
19. The Aba-Hpp linkage is also an attractive cyclization site because it is not subject to "racemization".
20. (a) Nitz, T. J.; Holt, E. M.; Rubin, B.; Stammer, C. H. J. Org. Chem. 1981, 46, 2667-2673.
21. (b) Arenal, I.; Bernabe, M.; Fernadez-Alvarez, E. An. Quim., Ser. C 1981, 77, 56-62.
22. (c) Makowski, M.; Rzezotarska, B.; Kubica, Z.; Pietrzynski, G.; Hetper, J. Liebigs Ann. Chem. 1986, 980-991.
23. Wissner, A.; Grudzinskas, C. V. J. Org. Chem. 1978, 43, 3972-3974.
24. Chen, S.-T.; Wu, S.-H.; Wang, K.-T. Synthesis 1989, 37-38.
25. (a) Makowski, M.; Rzeszotarska, B.; Kubica, Z.; Wieczorek, P. Liebigs Ann. Chem. 1984, 920-928.
26. (b) Smelka, L.; Rzeszotarska, B.; Pietrznski, G.; Kubica, Z. Liebigs Ann. Chem. 1988, 485-486.
27. A small amount of the corresponding (E)-isomer (ca. 5%) could be isolated. A similar result was obtained starting from either the pure (E)- or pure (Z)-isomer of 3.
28. Schmidt, U.; Weinbrenner, S. J. Chem. Soc., Chem. Commun. 1994, 1003-1004.
29. Cyclization of the (E)-isomer of 13 under the same conditions gave a mixture of 1 and 2 in good yield.
30. (a) Mazur, R. H.; Pilipauskas, D. R. Pept.: Synth, Struct., Funct., Proc. Am. Pept. Symp., 7th; Rich, D. H., Gross, E., Eds.; Pierce Chem. Co.: Rockford, IL, 1981; pp 81-84.
31. (b) Mazur, R. H.; Pilipauskas, D. R. Pept., Proc. Eur. Pept. Symp., 17th; 1982; Blaha, K., Malon, P., Eds.; de Gruyter: Berlin, 1983; pp 319-322.
32. Similar oxidation of the minor selenide isomer gave a 6:1 mixture of 1 and 2; oxidation of the other isomer gave only 2. Thus, assuming a stereoselective syn elimination of the selenides (via the corresponding selenoxides), the relative stereochemistry for major and minor isomers should be lk (i.e., syn PhSe and NH groups) and ul for the second major isomer. Phomalide and isophomalide are separable (PTLC), albeit with considerable difficulty and with low efficiency (i.e., mainly mixed fractions are obtained).
33. For a similar syn-elimination of sulfoxide derivatives of threonine, see ref 8a. For other examples of dehydroamino acid syntheses by selenoxide fragmentation, see: (a) Walter, R.; Roy, J. J. Org. Chem. 1971, 36, 2561-6563. (b) Reich, H. J.; Jasperse, C. P.; Renga, J. M. Ibid. 1986, 51, 2981-2988. (c) Hashimoto, K.; Sakai, M.; Okuno, T.; Shirahama, H. Chem. Commun. 1996, 1139-1140.
34. For a similar syn-elimination of sulfoxide derivatives of threonine, see ref 8a. For other examples of dehydroamino acid syntheses by selenoxide fragmentation, see: (a) Walter, R.; Roy, J. J. Org. Chem. 1971, 36, 2561-6563. (b) Reich, H. J.; Jasperse, C. P.; Renga, J. M. Ibid. 1986, 51, 2981-2988. (c) Hashimoto, K.; Sakai, M.; Okuno, T.; Shirahama, H. Chem. Commun. 1996, 1139-1140.
35. For a similar syn-elimination of sulfoxide derivatives of threonine, see ref 8a. For other examples of dehydroamino acid syntheses by selenoxide fragmentation, see: (a) Walter, R.; Roy, J. J. Org. Chem. 1971, 36, 2561-6563. (b) Reich, H. J.; Jasperse, C. P.; Renga, J. M. Ibid. 1986, 51, 2981-2988. (c) Hashimoto, K.; Sakai, M.; Okuno, T.; Shirahama, H. Chem. Commun. 1996, 1139-1140.
36. D, TLC and HPLC retention times) with an authentic sample.
37. Pedras, M. S. C.; Taylor, J. L.; Morales, V. M. Phytochemistry 1995, 38, 1215-1222.
38. Pedras, M. S. C.; Séguin-Swartz, G.; Abrams, S. R. Phytochemistry 1990, 29, 777-782.