High‐performance liquid chromatography quantification of enantiomers of a Dihydroxylated tetrahydrofuran natural product

Abstract

Both enantiomers of petromyroxol are putative pheromones in sea lamprey (Petromyzon marinus). Here, we describe the separation and quantification of the petromyroxol enantiomers using high-performance liquid chromatography tandem mass spectrometry. The separation was tested on a wide range of chiral columns with normal phases, and effects of the chromatographic parameters such as mobile phase and temperature on the separation were optimized. The AD-H column showed the best separation of enantiomers with n-hexane and ethanol as the mobile phase. The enantiomers were detected by multiple reaction monitoring with a positive atmospheric-pressure chemical ionization on triple quadrupole mass spectrometer. Validation revealed that the method was specific, accurate, and precise. The validated method was applied to measure the amount of petromyroxol enantiomers in water conditioned with sea lamprey larvae, the source of the putative pheromone. This method will be applied in quantifying the natural scalemic petromyroxol mixture, enabling further investigations of a rare non-racemic enantiomeric pheromone mixture in a vertebrate species.

Total Synthesis of (+)-Petromyroxol, (−)-iso-Petromyroxol, and Possible Diastereomers

“…Recently, a pair of two enantiomeric novel fatty acid enantiomers, named petromyroxol ( 1 ) and iso -petromyroxol ( 2 ) possessing cis - and trans -dihydroxytetrahydrofuran cores (Figure ), was isolated from larval sea lamprey-conditioned water. , The sea lamprey are parasitic fish widely distributed along the shores of northern/western Atlantic and the western Mediterranean Sea. They are also found in the shores of the great lakes and are considered as pests and known to cut back the indigenous fish populations.…”