Abstract
The hydrocarbons (3Z,6Z,9Z)-3,6,9-octadecatriene (3Z,6Z,9Z-18:H) and (3Z,6Z,9Z)-3,6,9-nonadecatriene (3Z,6Z,9Z-19:H) constitute the pheromone of the winter moth, Erannis bajaria. These compounds belong to a large group of lepidopteran pheromones which consist of unsaturated hydrocarbons and their corresponding oxygenated derivatives. The biosynthesis of such hydrocarbons with an odd number of carbons in the chain is well understood. In contrast, knowledge about the biosynthesis of even numbered derivatives is lacking. We investigated the biosynthesis of 3Z,6Z,9Z-18:H by applying deuterium-labeled precursors to females of E. bajaria followed by gas chromatography–mass spectrometry analysis of extracts of the pheromone gland. A mixture of deuterium-labeled [17,17,18,18-2H4]-3Z,6Z,9Z-18:H and the unlabeled 3Z,6Z,9Z-18:H was obtained after topical application and injection of (10Z,13Z,16Z)-[2,2,3,3-2H4]-10,13,16-nonadecatrienoic acid ([2,2,3,3-2H4]-10Z,13Z,16Z-19:acid) or (11Z,14Z,17Z)-[3,3,4,4-2H4]-11,14,17-icosatrienoic acid ([3,3,4,4-2H4]-11Z,14Z,17Z-20:acid). These results are consistent with a biosynthetic pathway that starts with α-linolenic acid (9Z,12Z,15Z-18:acid). Chain elongation leads to 11Z,14Z,17Z-20:acid, which is shortened by α-oxidation as the key step to yield 10Z,13Z,16Z-19:acid. This acid can be finally reduced to an aldehyde and decarbonylated or decarboxylated to furnish the pheromone component 3Z,6Z,9Z-18:H. A similar transformation of 11Z,14Z,17Z-20:acid yields the second pheromone component, 3Z,6Z,9Z-19:H.
References
Becker, D., Kimmel, T., Cyjon, R., Moore, I., Wysoki, M., Bestmann, H. J., Platz, H., Roth, K., and Vostrowsky, O. 1983. (3Z,6Z,9Z)-3,6,9-Nonadecatriene, a component of the sex pheromonal system of the Giant Looper, Boarmia (Ascotis) selenaria Schiffermüller (Lepidoptera: Geometridae). Tetrahedron Lett. 24:5503–5508.
Jurenka, R. 2004. Insect pheromone biosynthesis, pp. 97–132, in S., Schulz (ed.). The Chemistry of Pheromones and Other Semiochemicals I. Topics In Current Chemistry, vol. 239. Springer, Berlin Heidelberg New York.
Matsunaga, I., Yokotani, N., Gotoh, O., Kusunose, E., Yamada, M., and Ichihara, K. 1997. Molecular cloning and expression of fatty acid α-hydroxylase from Sphingomonas paucimobilis. J. Biol. Chem. 272:23592–23596.
Millar, J. G. 2000. Polyene hydrocarbons and epoxides: A second major class of lepidopteran sex attractant pheromones. Annu. Rev. Entomol. 45:575–604.
Park, M.-O. 2005. New pathway for long-chain n-alkane synthesis via 1-alcohol in Vibrio furnissii M1. J. Bacteriol. 187:1426–1429.
Reed, J. R., Quilici, D. R., Blomquist, G. J., and Reitz, R. C. 1995. Proposed mechanism for the cytochrome P450-catalyzed conversion of aldehydes to hydrocarbons in the house fly, Musca domestica. Biochemistry 34:16221–16227.
Rule, G. S. and Roelofs, W. L. 1989. Biosynthesis of sex pheromone components from linolenic acid in arctiid moths. Arch. Insect Biochem. Physiol. 12:89–97.
Szöcs, G., Tóth, M., Francke, W., Franke, S., and Plass, E. 1996. Homologous polyenic hydrocarbons in the sex pheromones of winter geometrids (Lepidoptera). Book of Abstracts, 13th Annual Meeting Int. Soc. Chem. Ecol. Prague, p. 178.
Taber, D. F. and Kong, S. 1997. Alkylation of acetonitrile. J. Org. Chem. 62:8575–8576.
Tvermyr, S. 1969. Sex pheromone in females of Erannis aurantiaria Hb. and Erannis defoliaria Cl. (Lep. Geometridae). Nor. Entomol. Tidsskr. 16:25–28.
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Goller, S., Szöcs, G., Francke, W. et al. Biosynthesis of (3Z,6Z,9Z)-3,6,9-Octadecatriene: The Main Component of the Pheromone Blend of Erannis bajaria . J Chem Ecol 33, 1505–1509 (2007). https://doi.org/10.1007/s10886-007-9324-z
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DOI: https://doi.org/10.1007/s10886-007-9324-z