Biosynthesis of (3Z,6Z,9Z)-3,6,9-Octadecatriene: The Main Component of the Pheromone Blend of Erannis bajaria

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-(2)H(4)]-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-(2)H(4)]-10,13,16-nonadecatrienoic acid ([2,2,3,3-(2)H(4)]-10Z,13Z,16Z-19:acid) or (11Z,14Z,17Z)-[3,3,4,4-(2)H(4)]-11,14,17-icosatrienoic acid ([3,3,4,4-(2)H(4)]-11Z,14Z,17Z-20:acid). These results are consistent with a biosynthetic pathway that starts with alpha-linolenic acid (9Z,12Z,15Z-18:acid). Chain elongation leads to 11Z,14Z,17Z-20:acid, which is shortened by alpha-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.