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The Pharmaceutical Society of Korea (대한약학회)
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Lipase Mediated Chiral Resoulution of 4-Arylthio-2-Butanol as an Intermediate for $\beta-Lactam$ Antibiotics

  • Published : 2003.11.01
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Abstract

This paper deals with chiral enzymatic resolution of 4-arylthio-2-butanols by lipase to prepare potential intermediates of $\beta$-lactam antibiotics. Among several lipases employed, lipase P type enzyme gave the highest ee value to prepare (R)-4-arylthio-2-butyl acetate. The enzymatic resolution of phenyl substituted alcohol (6a) using lipase P showed the highest ee value (99.7%) among those of 4-arylthio-2-butanol derivatives. Lipase P mediated hydrolysis of acylester 7a gave also (R)-alcohol 6a selectively. For determination of enantiomeric purity of these enzymatic resolved analytes, liquid chromatographic analysis was performed using two coupled Chiralcel OD and (R,R)-WhelkO chiral column.

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References

  1. Berks, A. H., Preparations of two pivotal intermediates for the synthesis of 1-$\beta$-methyl carbapenem antibiotics, Tetrahedron, 52, 331-375 (1996) https://doi.org/10.1016/0040-4020(95)00842-X
  2. Kim, B.-H. and Lee, W., Liquid chromatographic resolution of pyrethroic acids and their esters on chiral stationary phases. J. High Resol. Chromato., 21, 189-192 (1998) https://doi.org/10.1002/(SICI)1521-4168(19980301)21:3<189::AID-JHRC189>3.0.CO;2-3
  3. Lee, W., Separation of the enantiomers of amino acid esters as benzophenone imine derivatives using polysaccharide derived chiral stationary phases, Chromatographia, 49, 61-64 (1999) https://doi.org/10.1007/BF02467188
  4. Liu., H. and Cohen, T. (S)-(+)-5-(Phenylthio)-2-pentanol and (S)-(+)-4-(phenylthio)-2-butanol: Readily prepared, useful additions to the chirality pool. highly enantioselective syntheses of naturally occurring spiroketal pheromones. J. Org. Chem., 60, 2022-2025 (1995) https://doi.org/10.1021/jo00112a025
  5. Nakatsuka, T., Iwata, H., Tanaka, R., Imajo, S., and Ishiguro, M., A facile conversion of the phenylthio group to acetoxy by copper reagents for a practical synthesis of 4-acetoxyazetidin-2-one derivatives from (R)-butane-1,3-diol. J. Chem. Soc., Chem. Commun., 35, 662-664 (1991)
  6. Ohtsuka, Y., Katoh, O., Sugai, T., and Ohta, H., Preparation of sulfur-containing optically active secondary alcohols based on Pichia farinosa-catalyzed anti-Prelog-rule reduction as the key step, Bull. Chem. Soc. Jpn., 70, 483-491 (1997) https://doi.org/10.1246/bcsj.70.483
  7. Shimamoto, T., Inoue, H., Yoshida, T., Tanaka, R., Nakatsuka, T., and Ishiguro, M., Copper-assisted substitution reaction for phenylthio group of a 4-phenylthioazetidinone derivative, Tetrahedron Lett., 35, 5887-5888 (1994) https://doi.org/10.1016/S0040-4039(00)78210-4
  8. Sih, C. J., Process for preparing optically active $\alpha$-hydroxyalkene derivatives from racemic esters. EP 471531 (1992). Chem. Abstr., 117, 24775 (1992)
  9. Sugai, T., Ohtsuka, Y., and Ohta, H., Biocatalytic preparation of (R)-(-)-4-(phenylthio)-2-butanol and (R)-(-)-4-(phenylsulfonyl)-2-butanol by the sequential use of Pichia fannosa and Rhodococcus rhodochrous. Chem. Lett., 233-234 (1996)
  10. Wang, Y.-F., lalonde, J. J., Momongan, M., bergbreiter, D. E., and Wong, C.-H., Lipase-catalyzed irreversible transesterifications using enol esters as acylating reagents: preparative enantio- and regioselective synthesis of alcohols, glycerol derivatives, sugars and organometallics. J. Am. Chem. Soc., 7200-7205 (1988)
  11. Yamashita, K., Kawada, N., Hamaya, T., and Ueda, Y., Microbial reduction of 3-oxo-1-phenylthio-1-butene. JP 08196287. Chem. Abstr., 125, 245827 (1996)