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Enantioselectivity of enzymatic acylation of some structurally various racemic alcohols in anhydrous aprotic media

  • Chemistry of Natural Compounds and Bioorganic Chemistry
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Abstract

Partial acylation of (R,S)-3,7-dimethyloctan-1-ol (1) and (R,S)-7-methoxy-3,7-dimethyloctan-1-ol (2) with vinyl acetate catalyzed by the lipase fromCandida cylindracea affords in good yields the correspondingS-configured acetates with 92–98% enantiomeric excess (ee). Under similar conditions, racemic α-cyclogeraniol (3), drim-7-en-11-ol, methyl 4-(3-hydroxy-2-methylpropyl)benzoate, and its η6-chromium(tricarbonyl) complex (6) are acylated with rather poor (and, for the two latter, opposite) enantioselectivity, whereas (R,S)-2,4∶3,5-di-O-benzylidenexylitol remains unaffected. Racemic isoborneol (8) and 2-nitro-1-phenylethanol also remain almost or completely unconverted. Attempts to perform enantioselective acylation of alcohols 3 and 8 with Ac2O in the presence of porcine pancreatic lipase (PPL) proved equally unsuccessful. By contrast, the PPL-catalyzed acylation of alcohol 6 with vinyl acetate at 17% conversion affords the levorotatory acetate (S)-6a withca. 100%ee. PPL-Mediated partial acylation of (R,S)-pantolactone with Ac2O, followed by mild deacylation of the resultingR acetate, gives (R)-(-)-pantolactone of 97% enantiomeric purity in 60% overall yield.

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Authors and Affiliations

  1. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp, 117913, Moscow, Russian Federation

    G. D. Gamalevich & E. P. Serebryakov

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  1. G. D. Gamalevich
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  2. E. P. Serebryakov
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 175–186, January, 1997.

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Gamalevich, G.D., Serebryakov, E.P. Enantioselectivity of enzymatic acylation of some structurally various racemic alcohols in anhydrous aprotic media. Russ Chem Bull 46, 171–183 (1997). https://doi.org/10.1007/BF02495369

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