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exo-Brevicomin Biosynthesis in the Fat Body of the Mountain Pine Beetle, Dendroctonus ponderosae

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Abstract

exo-Brevicomin (exo-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]octane) is an important semiochemical for a number of beetle species, including the highly destructive mountain pine beetle, Dendroctonus ponderosae. It also has been found in other insects and even in the African elephant. Despite its significance, little is known about its biosynthesis. In order to fill this gap and to identify new molecular targets for potential pest management methods, we performed gas chromatography–mass spectrometry analyses of cell cultures and in vitro assays of various D. ponderosae tissues with exo-brevicomin intermediates, analogs, and inhibitors. We confirmed that exo-brevicomin was synthesized by “unfed” males after emerging from the brood tree. Furthermore, in contrast to the paradigm established for biosynthesis of monoterpenoid pheromone components in bark beetles, exo-brevicomin was produced in the fat body, and not in the anterior midgut. The first committed step involves decarboxylation or decarbonylation of ω-3-decenoic acid, which is derived from a longer-chain precursor via β-oxidation, to (Z)-6-nonen-2-ol. This secondary alcohol is converted to the known precursor, (Z)-6-nonen-2-one, and further epoxidized by a cytochrome P450 to 6,7-epoxynonan-2-one. The keto-epoxide is stable at physiological pH, suggesting that its final cyclization to form exo-brevicomin is enzyme-catalyzed. exo-Brevicomin production is unusual in that tissue not derived from ectoderm apparently is involved.

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Acknowledgments

We thank managers of the Whittell Forest for permission to collect beetles and members of CT’s and GJB’s labs for experimental and editing assistance. This work was supported by the USDA-AFRI (2005-04891) and USDA-NIFA (2009-05200), HATCH (NEV0339) and MacIntyre-Stennis (NEV0369) grants from the Nevada Agriculture Experiment Station, and an NIGMS grant (8 P20 GM103440-11) to Nevada INBRE from the NIH.

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Authors and Affiliations

  1. Department of Biochemistry and Molecular Biology, University of Nevada, Reno, Mail Stop 330, Reno, NV, 89557, USA

    Minmin Song, Andrew Gorzalski, Gary J. Blomquist & Claus Tittiger

  2. Department of Chemistry, University of Nevada, Reno, Reno, NV, 89557, USA

    Trang T. Nguyen, Xibei Liu & Christopher Jeffrey

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  1. Minmin Song
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  2. Andrew Gorzalski
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  3. Trang T. Nguyen
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  4. Xibei Liu
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  5. Christopher Jeffrey
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  6. Gary J. Blomquist
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  7. Claus Tittiger
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Correspondence to Claus Tittiger.

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Song, M., Gorzalski, A., Nguyen, T.T. et al. exo-Brevicomin Biosynthesis in the Fat Body of the Mountain Pine Beetle, Dendroctonus ponderosae . J Chem Ecol 40, 181–189 (2014). https://doi.org/10.1007/s10886-014-0381-9

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  • DOI: https://doi.org/10.1007/s10886-014-0381-9

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