Abstract
Gas chromatographic and mass spectroscopic analyses of extracts of cantharidin-containing meloid, clerid, and staphylinid beetles revealed the presence of minor to significant amounts of palasonin, previously only known from seeds and fruits of the Indian shrub Butea frondosa (Leguminaceae). Unlike (S)-(–)-palasonin (>99% ee) from B. frondosa, the insects produce palasonin of low ee with the (R)-(+)-enantiomer (0–50% ee) prevailing. The ee of palasonin from individual specimens of predatory insects (Trichodes apiarius), which acquire their chemical protection from cantharidin-producing insects, may vary considerably. The absolute configuration of (S)-(–)-palasonin, previously deduced from indirect chemical and spectroscopic methods, was confirmed by X-ray crystal structure analysis of a cyclic imide derived from (S)-(–)-palasonin and (S)-(–)-1-(4-nitrophenyl)-ethylamine.
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REFERENCES
Barua A. K., Chakrabarti, P., Das, K. G., and Nair, M. S.1970.Anewimide from Butea frondosa. Chem. Ind.43:1376.
Baumgarten, H. E. and Peterson, J.M.1960. Reactions of Amines.V. Synthesis of α-amino ketones. J. Am. Chem. Soc. 82:459–463.
Bologna, M. A. and Havelka, P.1984. Nuove segnalazioni di attrazione della cantharidina dei Meloidae su Coleotteri e Ditteri. Boll. Accoc. Rom. Entomol.39:77–82.
Carrel, J. E. and Eisner, T.1974. Cantharidin—potent feeding deterrent to insects. Science183:755–757.
Carrel, J. E., Doom, J. P., and McCormick, J. P.1986. Identification of cantharidin in false blister beetles (Coleoptera; Oedemeridae) from Florida USA. J. Chem. Ecol. 12:741–748.
Cohen, P.1989. The structure and regulation of protein phosphatases. Annu. Rev. Biochem. 58:453–508.
Dettner, K.1997. Inter-and intraspecific transfer of toxic insect compound cantharidin. Ecol. Stud.130:115–145, in: K. Dettner, G. Bauer, and W. Völkl (eds.). Vertical Food Web Interactions. Springer, Berlin.
Dettner, K., Schramm, S., Seidl, V., Klemm, K., G00c4;de, G., Fietz, O., and Boland, W.2001.Occurrence of the terpene anhydride palasonin and palasoninimide in blister beetle Hycleus lunataPall. (Coleoptera: Meloidae). Biochem. Syst. Ecol. In press.
Duetemeyer, J.1997. Zur Biosynthese von Cantharidin und Palasonin in Oedemera flavipes(Coleoptera: Oedemeridae) und in Butea frondosa(Fabaceae). PhD thesis. University of Bonn, Germany.
Eisner, T., Smedley, S. R., Young, D. K., Eisner, M., Roach, B., and Meinwald, J.1996. Chemicalbasis of courtship in a beetle (Neopyrochroa flabellata): Cantharidin as “nuptial gift.” Proc. Natl. Acad. Sci. USA93:6499–6503.
Fietz, O.2001. Cantharidin und Palasonin; neue Erkenntnisse zu zwei alten Wirkstoffen. PhD thesis. University of Jena, Germany.
Frenzel, M., Dettner, K., Wirth, D., Waibel, J., and Boland W.1992. Cantharidin analogues and their attractancy for ceratopogonid flies (Diptera: Ceratopogonidae). Experientia48:106–111.
Guha, P. K., Poi, R., and Bhattacharyya, A.1990. An imide from the pods of Butea monosperma. Phytochemistry29:2017.
Hemp, C. and Dettner, K.2001. Compilation of canthariphilous insects. Beitr. Entomol.51:231–245.
Hemp, C., Hemp, A., and Dettner, K.1999. Attraction of the colour beetle species Pallenothriocera rufimembrisby Cantharidin (Cleridae: Coleoptera). Entomol. Gener.24:115–123.
Holz, C., Streil, G., Dettner, K., Duetemeyer, J., and Boland, W.1994. Intersexual transfer of a toxic terpenoid during copulation and its paternal allocation to developmental stages: Quantification of cantharidin in cantharidin-producing oedemerids (Coleoptera: Oedemeridae) and canthariphilous pyrochroids (Coleoptera: Pyrochroidae). Z. Naturforsch.49C:856–864.
Horeau, A.1961. Principe et applications d'une nouvelle methode de determination des configurations dite par dedoublement partiel. Tetrahedron Lett.1961:506–512.
Juanjie, T., Youwei, Z., Shuyong, W., Zhengji, D., and Chuanxian, Z.1995. Investigation on the natural resources and utilization of the Chinese medicinal beetles. Acta Entomol. Sin. 38:324–331.
Klinker, R.1983. Eusphaleren, blütenbesuchende Staphyliniden; Zur Biologie der Käfer (Col., Staphylinidae). Dtsch. Entomol. Z.30:37–44.
Kumar, D., Mishra, S. K., Tandan, S. K., and Tripathi, H. C.1995. Possible mechanism of antihelmintic action of palasonin on Ascaridia galli. Indian J. Pharmacol.27:161–166.
Liu, X. H., Blazsek, I., Comisso, M., Legras, S., Marion, S., Quittet, P., Anjo, A., Wang, G. S., and Misset, J. L.1995. Effects of norcantharidin, a protein phosphatase type-2A inhibitor, on thegrowth of normal and malignant hematopoietic cells. Eur. J. Cancer31A:953–963.
Matsuzawa, M., Graziano, M. J., and Casida, J. E.1987. Endothall and cantharidin analogues relation of structure to herbicidal activity and mammalian toxicity. J. Agric. Food Chem.35:823–829.
McCormick, J. P. C. and James, E.1987. Cantharidin biosynthesis and function in meloid beetles, inG. Prestwich (ed.). Pheromone Biochemistry, Academic Press, Orlando, Florida.
McCormick, J. P., Carrel, J. E., and Doom, J. P.1986. Origin of oxygen atoms in cantharidin biosynthesized by beetles. J. Am. Chem. Soc.108:8071–8074.
Mehtar, R. K. and Pararsar, G. C.1966. Effect of Butea Frondosa, Veronianthelmintica and Carica papayaagainst oxyurides in mice. Indian Vet. J.43:744–748.
Otwinowski, Z. and Minor, W.1997. Processing of X-ray diffraction data collected in oscillation mode, pp. 307–326, inC. W. Carter and R. M. Sweet (eds.). Macromolecular Crystallography, Part A, Vol. 276. Academic Press, San Diego, California.
Peter, M. G., Snaizke, G., Snatzke, F., Nagarajan, K. N., and Schmid, H.1974. Über die absolute Konfiguration der Cantharsäure und des Palasonins. Helv. Chim. Acta57:32–64.
Raj, R. K. and Kurup, P.A.1967. Isolation and characterization of palasonin, an anthelmintic principle of the seeds of Butea frondosa. Indian J. Chem. 5:86–87.
Sheldrick, G. M.1990. Phase annealing in SHELX-90—direct methods for larger structures. Acta Crystallogr. Sec. A.46:467–473.
Sheldrick, G. M.1993. SHELXL-97. University of Göttingen, Germany.
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Fietz, O., Dettner, K., Görls, H. et al. (R)-(+)-Palasonin, a Cantharidin-Related Plant Toxin, Also Occurs in Insect Hemolymph and Tissues. J Chem Ecol 28, 1315–1327 (2002). https://doi.org/10.1023/A:1019561517040
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DOI: https://doi.org/10.1023/A:1019561517040