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J Chem Ecol

Title:		"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"
Author(s):		Gomes CMB; Souza JPA; Millar JG; Zarbin PHG;
Address:		"Laboratorio de Semioquimicos, Departamento de Quimica, Universidade Federal do Parana, UFPR, Caixa Postal19020, 81531-990, Curitiba, PR, Brazil. Department of Entomology, University of California, 92521, Riverside, CA, USA. Laboratorio de Semioquimicos, Departamento de Quimica, Universidade Federal do Parana, UFPR, Caixa Postal19020, 81531-990, Curitiba, PR, Brazil. pzarbin@ufpr.br"
Journal Title:		J Chem Ecol
Year:		2022
Volume:		20220716
Issue:		5-Jun
Page Number:		502 - 517
DOI:		10.1007/s10886-022-01371-5
ISSN/ISBN:		1573-1561 (Electronic) 0098-0331 (Linking)
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"
Keywords:		Animals Fatty Alcohols *Heteroptera/chemistry Male Pheromones *Sex Attractants/chemistry Stereoisomerism Chemical Ecology Chiral derivatization reagents Gas chromatography Pentatomidae Semiochemicals;
Notes:		"MedlineGomes, Carla M B Souza, Joao P A Millar, Jocelyn G Zarbin, Paulo H G eng 407312/2021-8/Conselho Nacional de Desenvolvimento Cientifico e Tecnologico/ 465511/2014-7/Conselho Nacional de Desenvolvimento Cientifico e Tecnologico/ 2022/07/17 J Chem Ecol. 2022 Jun; 48(5-6):502-517. doi: 10.1007/s10886-022-01371-5. Epub 2022 Jul 16"