Abstract
In a previous study, we reported the identification and synthesis of a male-specific sex pheromone component of the stink bug, Pellaea stictica, as the alcohol 2,4,8,13-tetramethyltetradecan-1-ol (1). To establish the correlation between the stereochemistry of the pheromone and its bioactivity, it first was necessary to determine its absolute configuration. For this purpose, a series of syntheses were designed to: (a) furnish a mixture of all possible stereoisomers; (b) a narrowed down group of diastereomers, and (c) one specific enantiomer. A crucial step in the syntheses involved a coupling reaction between two key intermediates: a phosphonium salt and an aldehyde, through a Wittig olefination. Nuclear magnetic resonance data of a mixture of the synthetic pheromone diastereomers and further comparison of GC retention times with that of the natural product by gas chromatography suggested that the methyl branches at C2 and C4 were in a syn relationship, reducing the possibilities to only four of the eight possible stereoisomers. Employing GC analysis, chiral derivatization reagents and synthetic (8R)-2,4-syn-1 it was possible to confirm the configuration of the methyl branch at C8 as R, reducing the number of possible stereoisomers to two. After enantioselective synthesis of (2R,4R,8R)-1, the absolute configurations of all methyl branches of the natural compound were confirmed as R, fully identifying the male-produced sex pheromone of P. stictica as (2R,4R,8R)-2,4,8,13-tetramethyltetradecan-1-ol.
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Acknowledgements
The authors thank the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Brazil), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and the Instituto Nacional de Ciências e Tecnologia de Semioquímicos na Agricultura (INCT) for financial support. We thank the Programa de Doutorado Sanduíche no Exterior (PDSE) for funding a visiting fellowship for Carla M. B. Gomes to the University of California, Riverside CA, USA.
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This research was supported by Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Brazil), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) (for fellowships of Gomes CMB and Souza JPA) and the Instituto Nacional de Ciências e Tecnologia de Semioquímicos na Agricultura (INCT).
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The synthesis and structural characterizations were performed by Gomes CMB and Souza JPA, supervised by Prof. Dr. Zarbin PHG and Prof. Dr. Millar JG. All authors contributed to the writing of manuscript. Prof. Dr. Zarbin PHG and Prof. Dr. Millar JG contributed with the laboratory facilities and financial structure for the development of the experiments.
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Gomes, C.M.B., Souza, J.P.A., Millar, J.G. et al. Determination of the Absolute Configuration of the Male-Produced Sex Pheromone of the Stink Bug Pellaea stictica, (2R,4R,8R)-2,4,8,13-Tetramethyltetradecan-1-ol by Stereoselective Synthesis Coupled with Enantiomeric Resolution. J Chem Ecol 48, 502–517 (2022). https://doi.org/10.1007/s10886-022-01371-5
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DOI: https://doi.org/10.1007/s10886-022-01371-5