Abstract
In the study of chiral biologically active compounds such as pheromones, the analysis of the stereoisomer composition is essential to gain more insight into their stereochemical diversity, which affects the pheromone communication channels and therefore the diversification of species. This mini-review summarizes the development of fluorescence derivatization reagents for high-performance liquid chromatographic (HPLC) determination of the absolute configuration and stereoisomer composition of natural products with a chiral branched alkyl chain. The diastereomeric separation of anteiso fatty acids bearing a branched methyl group up to the C-26 position was achieved by reversed-phase HPLC under very low column temperature conditions using (1S,2S)-2-(2,3-anthracenedicarboximido)cyclohexanol as a derivatization reagent, enabling fluorescent detection of these compounds at femtomole levels. This method was also applicable to chiral alcohols and amines with chiral branched methyl groups using similar reagents containing a carboxyl group. These reagents were successfully applied to determine the absolute configurations and stereoisomer composition of the chiral alkyl chain of natural compounds including some insect pheromones, miyakosyne A, and plakoside A. The combination of these reagents and two-dimensional HPLC constitutes a very powerful tool for the analysis of the stereoisomers of natural crude samples. Furthermore, the analysis of some natural bioactive substances using this method demonstrated that natural substances are not always optically pure, consisting instead of stereoisomer mixtures exhibiting stronger activity than optically pure enantiomers. These results cast doubts on the concept of biological homochirality and demonstrate that natural pheromones do not always show the highest activity among all stereoisomers.
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Acknowledgments
I deeply thank Prof. Kenji Mori to let me participate in his projects and for his encouragement and fruitful discussions on chiral chemistry, and I dedicate this article to him. Most of my application studies on chiral analysis of both synthetic and naturally occurring compounds would not have been achieved without his guidance and cooperation. I would like to thank Enago (WWW.enago.jp) for the English language review
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Akasaka, K. A Highly Selective and Sensitive Chiral Derivatization Method for High- Performance Liquid Chromatographic Determination of the Stereoisomer Composition of Natural Products With Chiral Branched Alkyl Chains. J Chem Ecol 48, 554–568 (2022). https://doi.org/10.1007/s10886-021-01345-z
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DOI: https://doi.org/10.1007/s10886-021-01345-z