title: Determination of the stereochemistry of the aggregation pheromone of harlequin bug, Murgantia histrionica.
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.
authors.affiliation: US Department of Agriculture, Agricultural Research Service, Invasive Insect Biocontrol and Behavior Laboratory, Beltsville, MD, 20705, USA, ashot.khrimian@ars.usda.gov.
authors.forename: Ashot
authors.initials: A
authors.lastname: Khrimian
authors.forename: Shyam
authors.initials: S
authors.lastname: Shirali
authors.forename: Karl E
authors.initials: KE
authors.lastname: Vermillion
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: Filadelfo
authors.initials: F
authors.lastname: Guzman
authors.forename: Kamlesh
authors.initials: K
authors.lastname: Chauhan
authors.forename: Jeffrey R
authors.initials: JR
authors.lastname: Aldrich
authors.forename: Donald C
authors.initials: DC
authors.lastname: Weber
mesh_terms: D000818:Animals; D002633:Chemotaxis; D002849:Chromatography, Gas; D018360:Crystallography, X-Ray; D020062:Heteroptera / Q000254:growth & development / Q000502:physiology*; D008297:Male; D010675:Pheromones / Q000378:metabolism*; D013237:Stereoisomerism
chemical_list: D010675:Pheromones