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Determination of the Stereochemistry of the Aggregation Pheromone of Harlequin Bug, Murgantia histrionica

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Abstract

Preparation of a complete stereoisomeric library of 1,10-bisaboladien-3-ols and selected 10,11-epoxy-1-bisabolen-3-ols was pivotal for the identification of the aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys. Herein, we describe syntheses of the remaining 10,11-epoxy-1-bisabolen-3-ols, and provide additional evidence on the assignment of relative and absolute configurations of these compounds by single-crystal X-ray crystallography of an intermediate, (3S,6R,7R,10S)-1-bisabolen-3,10,11-triol. To demonstrate the utility of this stereoisomeric library, we revisited the aggregation pheromone of the harlequin bug, Murgantia histrionica, and showed that the male-produced pheromone consists of two stereoisomers of 10,11-epoxy-1-bisabolen-3-ol. Employment of eight cis-10,11-epoxy-1-bisabolen-3-ol stereoisomeric standards, two enantioselective GC columns, and NMR spectroscopy enabled the identification of these compounds as (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol and (3S,6S,7R,10R)-10,11-epoxy-1-bisabolen-3-ol, which are produced by M. histrionica males in 1.4:1 ratio.

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Acknowledgments

We thank Dr. Jocelyn G. Millar, University of California, Riverside, for sharing 1H NMR spectrum of the murgantiol described in Zahn et al. 2008. We express our gratitude to Michael M. Athanas, Anthony DiMeglio, Matthew Klein, and Meiling Z. Webb, for collecting, rearing, and volatile collection of the insects.

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Author notes

  1. Jeffrey R. Aldrich

    Present address: Department of Entomology, University of California, Davis, CA, 95616, USA

Authors and Affiliations

  1. US Department of Agriculture, Agricultural Research Service, Invasive Insect Biocontrol and Behavior Laboratory, Beltsville, MD, 20705, USA

    Ashot Khrimian, Shyam Shirali, Filadelfo Guzman, Kamlesh Chauhan, Jeffrey R. Aldrich & Donald C. Weber

  2. US Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, Peoria, IL, 61604, USA

    Karl E. Vermillion

  3. Department of Chemistry, Johns Hopkins University, Baltimore, MD, 21218, USA

    Maxime A. Siegler

Authors
  1. Ashot Khrimian
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  2. Shyam Shirali
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  3. Karl E. Vermillion
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  4. Maxime A. Siegler
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  5. Filadelfo Guzman
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  6. Kamlesh Chauhan
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  7. Jeffrey R. Aldrich
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  8. Donald C. Weber
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Correspondence to Ashot Khrimian.

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Khrimian, A., Shirali, S., Vermillion, K.E. et al. Determination of the Stereochemistry of the Aggregation Pheromone of Harlequin Bug, Murgantia histrionica . J Chem Ecol 40, 1260–1268 (2014). https://doi.org/10.1007/s10886-014-0521-2

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  • DOI: https://doi.org/10.1007/s10886-014-0521-2

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