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.
- Publication:
-
Journal of Chemical Ecology
- Pub Date:
- December 2014
- DOI:
- Bibcode:
- 2014JCEco..40.1260K
- Keywords:
-
- Stink bug;
- Aggregation pheromone;
- (1S;
- 4S)-4-((R)-4-((S)-3;
- 3-dimethyloxiran-2-yl)butan-2-yl)-1-methylcyclohex-2-enol;
- (1S;
- 4S)-4-((R)-4-((R)-3;
- 3-dimethyloxiran-2-yl)butan-2-yl)-1-methylcyclohex-2-enol;
- Hemiptera;
- Pentatomidae