Preparation of single-enantiomer 2-methyl-4-heptanol, a pheromone of Metamasius hemipterus, using ( S)-2-methoxy-2-(1-naphthyl)propionic acid

Abstract

To investigate the resolution of secondary alcohols using 2-methoxy-2-(1-naphthyl)propionic acid (MαNP acid), 2-methyl-4-heptanol, one of the aggregation pheromones of Metamasius hemipterus, was resolved using ( S)-MαNP acid. As a chiral-resolving agent, MαNP acid is superior to 3,3,3-trifluoro-2-methoxy-2-phenylpropionic acid (MTPA) in terms of HPLC separation and NMR shielding. A better separation of diastereomeric MαNP esters was observed when n-hexane–THF was used as the eluent for silica gel HPLC. The solvolysis of the diastereomeric MαNP esters gave ( R)-2-methyl-4-heptanol and its enantiomer; enantiopure ( S)-MαNP acid was also recovered. In addition, the preferred conformation of the MαNP ester was confirmed using methyl ( R)-3-hydroxyvalerate as an authentic compound.