Facile Synthesis of Both Enantiomers of (Z)-1,5-Octadien-3-ol (Oyster Alcohol) and Its Identification from the Pacific Oyster Crassostrea gigas

J Oleo Sci. 2023;72(7):725-732. doi: 10.5650/jos.ess23032.

Abstract

The aim of this study was to present a facile protocol for preparation of both enantiomerically pure forms of (Z)-1,5-octadien-3-ol with lipases and to identify the stereochemistry of oyster alcohol from Crassostrea gigas. The asymmetric hydrolysis of (±)-(Z)-1,5-octadien-3-yl acetate with CHIRAZYME L-2 afforded the (R)-alcohol with ≧99% ee in 37.8% conversion. On the other hand, the first asymmetric acylation of the alkadienol with lipase PS recovered the (S)-alcohol with 79.5% ee in 47.8% conversion. Then, the second asymmetric acylation of the recovered (S)-alcohol with lipase PS gave the remaining (S)alcohol with ≧99% ee in 14.1% conversion. Thus, we have successfully prepared both enantiomerically pure forms of (Z)-1,5-octadien-3-ol with high ee (≧99%) separately. On the other hand, oyster alcohol in the extract from C. gigas was purified by silica gel column chromatography and the structure was confirmed by 1H- and 13C-nuclear magnetic resonance spectra. Furthermore, the stereochemistry of oyster alcohol was decided as the (R)-form from the specific rotation and its optical purities were determined as 20.45 ± 0.2% ee by a chiral gas chromatograph/mass spectrometry for the first time.

Keywords: chiral aroma; kinetic resolution; lipase; oyster.

MeSH terms

  • Acylation
  • Animals
  • Crassostrea*
  • Ethanol
  • Gas Chromatography-Mass Spectrometry
  • Lipase

Substances

  • Ethanol
  • Lipase