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Journal of Chemical Ecology

, Volume 44, Issue 5, pp 436–443 | Cite as

Structure-Activity Studies of Semiochemicals from the Spider Orchid Caladenia plicata for Sexual Deception

  • Bjorn Bohman
  • Amir Karton
  • Gavin R. Flematti
  • Adrian Scaffidi
  • Rod Peakall
Article

Abstract

Sexually deceptive orchids attract specific pollinators by mimicking insect sex pheromones. Normally this mimicry is very specific and identical compounds have been identified from orchids and matching females of the pollinators. In this study, we conduct a detailed structure-activity investigation on isomers of the semiochemicals involved in the sexual attraction of the male pollinator of the spider orchid Caladenia plicata. This orchid employs an unusual blend of two biosynthetically unrelated compounds, (S)-β-citronellol and 2-hydroxy-6-methylacetophenone, to lure its Zeleboria sp. thynnine wasp pollinator. We show that the blend is barely attractive when (S)-β-citronellol is substituted with its enantiomer, (R)-β-citronellol. Furthermore, none of the nine-possible alternative hydroxy-methylacetophenone regioisomers of the natural semiochemical are active when substituted for the natural 2-hydroxy-6-methylacetophenone. Our results were surprising given the structural similarity between the active compound and some of the analogues tested, and results from previous studies in other sexually deceptive orchid/wasp systems where substitution with analogues was possible. Interestingly, high-level ab initio and density functional theory calculations of the hydroxy-methylacetophenones revealed that the active natural isomer, 2-hydroxy-6-methylacetophenone, has the strongest intramolecular hydrogen bond of all regioisomers, which at least in part may explain the specific activity.

Keywords

Caladenia Sexual deception Pollination Structure-activity Isomers Hydrogen bonding 

Notes

Acknowledgements

BB, GRF, and RP acknowledge the Australian Research Council for funding (DE160101313, FT110100304, LP130100162 and DP150102762). The authors acknowledge the facilities, and the scientific and technical assistance of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy, Characterisation & Analysis, The University of Western Australia, a facility funded by the University, State and Commonwealth Governments. Alyssa Weinstein is thanked for field and laboratory assistance. RP was hosted as a visiting fellow by UWA while completing this study.

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Bjorn Bohman
    • 1
    • 2
    • 3
  • Amir Karton
    • 1
  • Gavin R. Flematti
    • 1
  • Adrian Scaffidi
    • 1
  • Rod Peakall
    • 1
    • 2
  1. 1.School of Molecular SciencesThe University of Western AustraliaCrawleyAustralia
  2. 2.Research School of BiologyThe Australian National UniversityActonAustralia
  3. 3.Research School of ChemistryThe Australian National UniversityActonAustralia

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