Journal of Chemical Ecology

, Volume 40, Issue 11–12, pp 1260–1268 | Cite as

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

  • Ashot KhrimianEmail author
  • Shyam Shirali
  • Karl E. Vermillion
  • Maxime A. Siegler
  • Filadelfo Guzman
  • Kamlesh Chauhan
  • Jeffrey R. Aldrich
  • Donald C. Weber


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.


Stink bug Aggregation pheromone (1S,4S)-4-((R)-4-((S)-3,3-dimethyloxiran-2-yl)butan-2-yl)-1-methylcyclohex-2-enol (1S,4S)-4-((R)-4-((R)-3,3-dimethyloxiran-2-yl)butan-2-yl)-1-methylcyclohex-2-enol Hemiptera Pentatomidae 



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.

Supplementary material

10886_2014_521_MOESM1_ESM.pdf (102 kb)
ESM 1 (PDF 101 kb)


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Copyright information

© Springer Science+Business Media New York (outside the USA) 2014

Authors and Affiliations

  • Ashot Khrimian
    • 1
    Email author
  • Shyam Shirali
    • 1
  • Karl E. Vermillion
    • 2
  • Maxime A. Siegler
    • 3
  • Filadelfo Guzman
    • 1
  • Kamlesh Chauhan
    • 1
  • Jeffrey R. Aldrich
    • 1
    • 4
  • Donald C. Weber
    • 1
  1. 1.US Department of Agriculture, Agricultural Research ServiceInvasive Insect Biocontrol and Behavior LaboratoryBeltsvilleUSA
  2. 2.US Department of Agriculture, Agricultural Research ServiceNational Center for Agricultural Utilization ResearchPeoriaUSA
  3. 3.Department of ChemistryJohns Hopkins UniversityBaltimoreUSA
  4. 4.Department of EntomologyUniversity of CaliforniaDavisUSA

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