Abstract
Resolution of insect pheromonal cis-epoxydiene racemates derived from (Z,Z,Z)-3,6,9-trienes was examined with a reversed-phase chiral HPLC column. The results showed that a Chiralcel OJ-R column was suitable for separating the enantiomers having a C17–C23 unsaturated straight chain except for 9,10-epoxydienes with a C21–C23 chain. To determine the absolute configuration of the separated enantiomers, each of the optically active epoxydienes was hydrogenated over Pd-BaSO4 and its behavior was examined on this chiral column by cochromatography with the corresponding chiral epoxy compound having a saturated chain, which was prepared via a Sharpless epoxidation reaction. This analysis showed that the dextrorotatory C17–C23 3,4- and 6,7-epoxydienes and C17–C20 9,10-epoxydienes with shorter R ts possess (3S,4R)-, (6S,7R)-, and (9R,10S) configurations, respectively, and the levorotatory enantiomers with longer R ts possess the opposite configuration. An abdominal tip extract of the mulberry looper, Hemerophila artilineata Butler (Lepidoptera: Geometridae: Ennominae), included (9S,10R)-(Z,Z)-cis-9,10-epoxy-3,6-octadecadiene as a main sex pheromone component. The synthetic (9S,10R)-9,10-epoxydiene, rather than its antipode, elicited strong antennal and behavioral responses from the male moths in electrophysiological and field tests.
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Pu, GQ., Yamamoto, M., Takeuchi, Y. et al. Resolution of Epoxydienes by Reversed-Phase Chiral HPLC and its Application to Stereochemistry Assignment of Mulberry Looper Sex Pheromone. J Chem Ecol 25, 1151–1162 (1999). https://doi.org/10.1023/A:1020894128395
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DOI: https://doi.org/10.1023/A:1020894128395