title: Discovery of the aggregation pheromone of the brown marmorated stink bug (Halyomorpha halys) through the creation of stereoisomeric libraries of 1-bisabolen-3-ols.
abstract: We describe a novel and straightforward route to all stereoisomers of 1,10-bisaboladien-3-ol and 10,11-epoxy-1-bisabolen-3-ol via the rhodium-catalyzed asymmetric addition of trimethylaluminum to diastereomeric mixtures of cyclohex-2-enones 1 and 2. The detailed stereoisomeric structures of many natural sesquiterpenes with the bisabolane skeleton were previously unknown because of the absence of stereoselective syntheses of individual stereoisomers. Several of the bisabolenols are pheromones of economically important pentatomid bug species. Single-crystal X-ray crystallography of underivatized triol 13 provided unequivocal proof of the relative and absolute configurations. Two of the epoxides, (3S,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (3) and (3R,6S,7R,10S)-10,11-epoxy-1-bisabolen-3-ol (4), were identified as the main components of a male-produced aggregation pheromone of the brown marmorated stink bug, Halyomorpha halys, using GC analyses on enantioselective columns. Both compounds attracted female, male, and nymphal H. halys in field trials. Moreover, mixtures of stereoisomers containing epoxides 3 and 4 were also attractive to H. halys, signifying that the presence of additional stereoisomers did not hinder attraction of H. halys and relatively inexpensive mixtures can be used in monitoring, as well as control strategies. H. halys is a polyphagous invasive species in the U.S. and Europe that causes severe injury to fruit, vegetables, and field crops and is also a serious nuisance pest.
authors: U.S. Department of Agriculture, Agricultural Research Service , Beltsville Area, IIBBL, Maryland 20705, United States.
authors: Ashot
authors: A
authors: Khrimian
authors: Aijun
authors: A
authors: Zhang
authors: Donald C
authors: DC
authors: Weber
authors: Hsiao-Yung
authors: HY
authors: Ho
authors: Jeffrey R
authors: JR
authors: Aldrich
authors: Karl E
authors: KE
authors: Vermillion
authors: Maxime A
authors: MA
authors: Siegler
authors: Shyam
authors: S
authors: Shirali
authors: Filadelfo
authors: F
authors: Guzman
authors: Tracy C
authors: TC
authors: Leskey
mesh_terms: D000818:Animals; D018360:Crystallography, X-Ray; D005260:Female; D020062:Heteroptera / Q000737:chemistry*; D058865:Introduced Species; D008297:Male; D008968:Molecular Conformation; D015394:Molecular Structure; D010675:Pheromones / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D012717:Sesquiterpenes / Q000737:chemistry / Q000302:isolation & purification* / Q000494:pharmacology; D013237:Stereoisomerism
chemical_list: D010675:Pheromones; D012717:Sesquiterpenes