Abstract
Adults of the longhorned beetle, Chloridolum loochooanum Gressitt (Coleoptera: Cerambycidae) emit a white frothy secretion from their metasternal glands. This defensive substance contains cyclopentanoid monoterpenoids (iridodials), whose structures were elucidated by gas chromatography-mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR) analyses that compared the naturally occurring structures with synthesized versions. Optically active citronellals, [(S)-, (R)-, and (S)/(R)- mixture], were used as starting materials for synthesizing the corresponding iridodials for the determination of the absolute configuration of the natural product. The retention time of (2S)-iridodial, derived from (S)-citronellal, corresponded to that of C. loochooanum iridodial by enantioselective GC analysis. Thus, we suggest that the absolute configuration of C. loochooanum iridodial is (1R,2S,5S)-iridodial.
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Acknowledgments
We thank Dr. Kamlesh R. Chauhan for donation of synthetic (1R,2S,5R,8R)-, and (1R,2S,5R,8S)-iridodials for comparison with C. loochooanum iridodials. We also thank Dr. Motoko Tagawa for valuable advice on this work. This work was supported in part by a Grant-in-Aid for Scientific Research (nos. 16780130, 19580197) from the Japan Society for the Promotion of Science.
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Ohmura, W., Hishiyama, S., Nakashima, T. et al. Chemical Composition of the Defensive Secretion of the Longhorned Beetle, Chloridolum loochooanum . J Chem Ecol 35, 250–255 (2009). https://doi.org/10.1007/s10886-009-9591-y
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DOI: https://doi.org/10.1007/s10886-009-9591-y