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Discovery of the Aggregation Pheromone of the Brown Marmorated Stink Bug (Halyomorpha halys) through the Creation of Stereoisomeric Libraries of 1-Bisabolen-3-ols

Ashot Khrimian, Aijun Zhang, Donald C. Weber, Hsiao-Yung Ho, Jeffrey R. Aldrich, Karl E. Vermillion, Maxime A. Siegler, Shyam Shirali, Filadelfo Guzman, Tracy C. Leskey
Journal of natural products 2014 v.77 no.7 pp. 1708-1717
Halyomorpha halys, X-ray diffraction, aggregation pheromones, catalysts, catalytic activity, epoxides, females, field experimentation, gas chromatography, insect attractants, invasive species, males, monitoring, nymphs, rhodium, sesquiterpenoids, stereoisomers
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. Halyomorpha 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.