USDA Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 North University Street, Peoria, Illinois 61604, USA.
J Nat Prod. 2011 Apr 25;74(4):585-95. doi: 10.1021/np100608p. Epub 2011 Feb 22.
Flea beetles in several genera are known to possess male-specific sesquiterpenes, at least some of which serve as aggregation pheromones that attract both sexes. In continuing research on the chemical ecology of Phyllotreta flea beetles, six new male-specific sesquiterpenes were identified, one from P. striolata (hydroxyketone 9) and five from P. pusilla (aldehydes 10-12 and 14 and alcohol 13); both species are crop pests. The minute amounts from beetles provided mass spectra and chromatographic data but were insufficient for complete structure determination. However, it was discovered that the new compounds could all be produced by applying organic reactions to previously identified flea beetle sesquiterpenes, and the resulting, larger amounts of material permitted definitive structure analysis by NMR. Molecular modeling was used in conjunction with NMR to define relative configurations of several newly created stereogenic centers. The absolute configurations of natural 9-14 were established by chiral gas chromatography/mass spectrometry. In electrophysiological tests (GC-EAD) conducted with P. striolata, compound 9 was detected with high sensitivity by the beetle antennae, which is consistent with a pheromonal function. The research opens new possibilities for using behavioral chemicals to monitor or manage these pest species.
已知一些蚤蝇属的蚤蝇具有雄性特异性倍半萜，其中至少一些作为聚集信息素吸引雌雄两性。在对 Phyllotreta 蚤蝇的化学生态学的持续研究中，鉴定出了六种新的雄性特异性倍半萜，一种来自 P. striolata（羟基酮 9），五种来自 P. pusilla（醛 10-12 和 14 以及醇 13）；这两个物种都是作物害虫。从甲虫中提取的微量物质提供了质谱和色谱数据，但不足以完全确定结构。然而，人们发现，通过将有机反应应用于先前鉴定的蚤蝇倍半萜，可以产生所有新化合物，并且产生的大量物质允许通过 NMR 进行明确的结构分析。分子建模与 NMR 结合使用，确定了几个新创建的手性中心的相对构型。天然 9-14 的绝对构型通过手性气相色谱/质谱法确定。在用 P. striolata 进行的电生理测试（GC-EAD）中，化合物 9 被甲虫触角高度敏感地检测到，这与信息素功能一致。这项研究为使用行为化学物质来监测或管理这些害虫物种开辟了新的可能性。
