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A Novel Trisubstituted Tetrahydropyran as a Possible Pheromone Component for the South American Cerambycid Beetle Macropophora accentifer

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Abstract

A novel trisubstituted tetrahydropyran was isolated and identified from the sex-specific volatiles produced by males of the cerambycid beetle Macropophora accentifer (Olivier), a serious pest of citrus and other fruit crops in South America. The compound was the major component in the headspace volatiles, and it was synthesized in racemic form. However, in field trials, the racemate was only weakly attractive to beetles of both sexes, suggesting that attraction might be inhibited by the presence of the “unnatural” enantiomer in the racemate. Alternatively, the male-produced volatiles contained a number of minor and trace components, including a compound tentatively identified as a homolog of the major component, as well as a number of unsaturated 8-carbon alcohols and aldehydes. Further work is required to conclusively identify and synthesize these minor components, to determine whether one or more of them are crucial components of the active pheromone blend for this species.

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Acknowledgements

We thank Citrosuco S/A Agroindústria for allowing access to the experimental sites at Rio Pardo Farm and for providing logistical support to this research. A special thank you to Germano Pires Galhardo and Denis Rogério Marin for assisting with the field experiments and for providing the infested citrus trunks. We also thank Antonio Santos-Silva (Museum of Zoology, USP) for identifying the cerambycid species. Field collections of the study species in Brazil were conducted under SISBIO permit #46395 from the Brazilian Ministry of the Environment. This work was registered with the National System for the Management of Genetic Heritage and Associated Traditional Knowledge (SisGen, Brazil) under #AE3897B.

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Funding

This work was supported by Instituto Nacional de Ciencia e Tecnologia de Semioquímicos na Agricultura (Fundação de Amparo à Pesquisa do Estado de São Paulo and Conselho Nacional de Desenvolvimento Científico e Tecnológico, grant #s 2014/50871-0 and 465511/2014-7 to JMB) and the United States Department of Agriculture – Animal and Plant Health Inspection Service (grant #s 15, 16, 17, 18, 19, 20, and 21-8130-1422-CA to JGM and LMH, and grant # 21-8130-0909-CA to WDS).

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Authors and Affiliations

  1. Department of Entomology and Acarology, University of São Paulo, Piracicaba, SP, 13418900, Brazil

    Weliton D. Silva & José Maurício S. Bento

  2. Departments of Entomology and Chemistry, University of California, Riverside, CA, 92521, USA

    Yunfan Zou & Jocelyn G. Millar

  3. Department of Entomology, University of Illinois at Urbana-Champaign, Urbana, IL, 61801, USA

    Lawrence M. Hanks

Authors
  1. Weliton D. Silva
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  2. Yunfan Zou
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  3. Lawrence M. Hanks
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  4. José Maurício S. Bento
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  5. Jocelyn G. Millar
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Contributions

All authors contributed to the study conception and design. WDS collected insects, prepared extracts, carried out initial analyses, and carried out field trials. JGM identified the compound and carried out the first synthesis. YZ carried out the synthesis of the pure diastereomer. WDS and LMH carried out the data analyses, and WDS, YZ, and JGM drafted the manuscript, which was then edited by all authors. Funding was obtained by JGM, LMH, and JMB.

Corresponding author

Correspondence to Jocelyn G. Millar.

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The authors declare no conflicts of interest.

Additional information

Dedicated to the memory of Professor Kenji Mori

Supplementary Information

Supplementary online information includes the synthetic procedures for the nonstereoselective synthesis of the major insect-produced compound, the proton and gCOSY NMR spectra of the isolated compound in CD2Cl2, the GC-EAD analyses of synthetic THP, the proton spectra of the synthesized THP compound in both CD2Cl2 and C6D6 solvents, the EI mass spectra of minor components A–G, I, and K in the volatiles from male beetles, and analyses of insect-produced and synthetic racemic THP on a chiral stationary phase GC column..

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Silva, W.D., Zou, Y., Hanks, L.M. et al. A Novel Trisubstituted Tetrahydropyran as a Possible Pheromone Component for the South American Cerambycid Beetle Macropophora accentifer. J Chem Ecol 48, 569–582 (2022). https://doi.org/10.1007/s10886-022-01362-6

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