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

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.

Keywords

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 

Notes

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.

Supplementary material

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

References

  1. Aldrich JR, Oliver JE, Lusby WR, Kochansky JP, Lockwood JA (1987) Pheromone strains of the cosmopolitan pest Nezara viridula (Heteroptera: Pentatomidae). J Exp Zool 244:171–175CrossRefGoogle Scholar
  2. Aldrich JR, Lusby WR, Marron BE, Nicolaou KC, Hoffmann MP, Wilson LT (1989) Pheromone blends of green stink bugs and possible parasitoid selection. Naturwissenschaften 76:173–175CrossRefGoogle Scholar
  3. Baker R, Borges M, Cooke NG, Herbert RH (1987) Identification and synthesis of (Z)-(1′S,3′R,4′)-(−)-2-(3′,4′-epoxy-4′-methylcyclohexyl)-6-methylhepta-2,5-diene, the sex pheromone of the southern green stink bug, Nezara viridula (L.). J Chem Soc Chem Commun 414–416Google Scholar
  4. Blair M, Tuck KL (2009) A new diastereoselctive entry to the (1S,4R)- and (1S,4S)-isomers of 4-isopropyl-1-methyl-2-cyclohexen-1-ol, aggregation pheromones of the ambrosia beetle Platypus quercivorus. Tetrahedron Asymmetry 20:2149–2153CrossRefGoogle Scholar
  5. Borges M, Birkett M, Aldrich JR, Oliver JE, Chiba M, Murata Y, Laumann RA, Barrigossi JA, Pickett JA, Moraes MCB (2006) Sex attractant pheromone from the rice stalk stink bug, Tibraca limbativentris Stal. J Chem Ecol 32:2749–2764PubMedCrossRefGoogle Scholar
  6. de Oliveira MWM, Borges M, Andrade CKZ, Lauman RA, Barrigossi JAF, Blassioli-Moraes MC (2013) Zingiberenol, (1S,4R,1′S)-4-(1′,5′-dimethylhex-4′-enyl)-1-methylcyclohex-2-en-1-ol, identified as the sex pheromone produced by males of the rice stink bug Oebalus poecilus (Heteroptera: Pentatomidae). J Agric Food Chem 61:7777–7785PubMedCrossRefGoogle Scholar
  7. Flack HD (1983) On enantiomorph-polarity estimation. Acta Cryst A39:876–881CrossRefGoogle Scholar
  8. Frater G, Müller U (1989) Synthesis of (+)-(4S,8R)-8-epi- and (−)-(4R,8S)-4-epi-β-bisabolol. Helv Chim Acta 72:653–658CrossRefGoogle Scholar
  9. Hooft RWW, Straver LH, Spek AL (2008) Determination of absolute structure using Bayesian statistics on Bijvoet differences. J Appl Crystallogr 41:96–103PubMedCentralPubMedCrossRefGoogle Scholar
  10. Khrimian A, Zhang A, Weber DC, Ho H-Y, Aldrich JR, Vermillion KE, Siegler MA, Shirali S, Guzman F, Leskey TC (2014) Discovery of the aggregation pheromone of the brown marmorated stink bug (Halyomorpha halys) through the creation of stereoisomeric libraries of 1-bisabolen-3-ols. J Nat Prod 77:1708–1717PubMedCrossRefGoogle Scholar
  11. Leal WS, Kuwahara S, Shi XA, Higuchi H, Marino CEB, Ono M, Meinwald J (1998) Male-released sex pheromone of the stink bug Piezodorus hybneri. J Chem Ecol 24:1817–1829CrossRefGoogle Scholar
  12. McBrien HL, Millar JG, Gottlieb L, Chen X, Rice RE (2001) Male-produced sex attractant pheromone of the green stink bug Acrosternum hilare (Say). J Chem Ecol 27:1821–1839PubMedCrossRefGoogle Scholar
  13. McBrien HL, Millar JG, Rice RE, McElfresh JS, Cullen E, Zalom FG (2002) Sex attractant pheromone of the red-shouldered stink bug Thyanta pallidovirens: a pheromone blend with multiple redundant components. J Chem Ecol 28:1797–1817PubMedCrossRefGoogle Scholar
  14. Moore CJ, Possner S, Hayes P, Paddon-Jones GC, Kitching W (1999) An asymmetric dihydroxylation route to (3R,5E)-2,6-dimethyl-2,3-epoxyocta-5,7-diene: the major volatile component from male fruit-spotting bugs. J Org Chem 64:9742–9744CrossRefGoogle Scholar
  15. Sharpless KB, Amberg W, Bennani YL, Crispino GA, Hartung J, Jeong K-S, Kwong H-L, Morikawa K, Wang Z-M, Xu D, Zhang X-L (1992) The osmium-catalyzed asymmetric dihydroxylation: a new ligand class and a process improvement. J Org Chem 57:2768–2771CrossRefGoogle Scholar
  16. Sheldrick GM (2008) A short history of SHELX. Acta Crystallogr A64:112–122CrossRefGoogle Scholar
  17. Terhune SJ, Hogg JW, Bromstein AC, Lawrence BM (1974) Four new sesquiterpene analogs of common monoterpenes. Can J Chem 53:3287–3293Google Scholar
  18. Wallingford AK, Kuhar TP, Schultz PB, Freeman JH (2011) Harlequin bug biology and pest management in Brassicaceous crops. J Integr Pest Mgmt 2:H1–H4CrossRefGoogle Scholar
  19. Weber DC, Cabrera Walsh G, DiMeglio AS, Athanas MM, Leskey TC, Khrimian A (2014) Attractiveness of harlequin bug, Murgantia histrionica (Hemiptera: Pentatomidae), aggregation pheromone: field response to isomers, ratios and dose. J Chem Ecol, in pressGoogle Scholar
  20. Zahn DK, Moreira JA, Millar JG (2008) Identification, synthesis, and bioassay of a male-specific aggregation pheromone from the harlequin bug, Murgantia histrionica. J Chem Ecol 34:238–251PubMedCrossRefGoogle Scholar
  21. Zahn DK, Moreira JA, Millar JG (2012) Erratum to: identification, synthesis, and bioassay of a male-specific aggregation pheromone from the harlequin bug, Murgantia histrionica. J Chem Ecol 38:126CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  • Ashot Khrimian
    • 1
  • 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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