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Regioselective Enzymatic Acylation of Methyl Shikimate. Influence of Acyl Chain Length and Solvent Polarity on Enzyme Specificity

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Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, 33071-Oviedo, Spain [email protected]
Cite this: J. Org. Chem. 2002, 67, 14, 4978–4981
Publication Date (Web):May 21, 2002
Copyright © 2002 American Chemical Society

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    Abstract Image

    Candida antarctica lipase A (CAL-A) selectively catalyzes the acylation at the secondary C-4 hydroxyl group of methyl shikimate (2), which possesses three secondary hydroxyl groups, the C-3 allylic one being chemically more reactive. The effect both of the acyl group of the acylating agents and of the solvent polarity has been studied. The selectivity of CAL-A is almost complete with acyl donors that possess short chains. However, when acyl donors have longer chains, better results are obtained by C. antarctica lipase B (CAL-B).


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    Complete 1H and 13C NMR spectral data in addition to mp, IR, microanalysis, optical rotation, and MS data for major monoacylated derivatives; the level of purity is indicated by the inclusion of microanalysis and copies of 1H and 13C NMR spectra. This material is available free of charge via the Internet at

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    10. Eduardo García-Urdiales, Nicolás Ríos-Lombardía, Juan Mangas-Sánchez, Vicente Gotor-Fernández, Vicente Gotor. Influence of the Nucleophile on the Candida antarctica Lipase B-Catalysed Resolution of a Chiral Acyl Donor. ChemBioChem 2009, 10 (11) , 1830-1838.
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    12. Zhao‐Yu Wang, Min‐Hua Zong. Recognition of acyl donors by lipase CAL‐B in the acylation of 6‐azauridine. Biotechnology Progress 2009, 25 (3) , 784-791.
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    14. Chao Li, Hai-Yang Wang, Na Wang, Yu-Guo Fang, Xi Chen, Xiao-Qi Yu. Highly regioselective enzymatic synthesis of polymerizable derivatives of methyl shikimate. Bioorganic & Medicinal Chemistry Letters 2007, 17 (24) , 6687-6690.
    15. Jing Quan, Na Wang, Xiao-Qing Cai, Qi Wu, Xian-Fu Lin. Controllable selective enzymatic synthesis of N-acyl and O-acylpropranolol vinyl esters and preparation of polymeric prodrug of propranolol. Journal of Molecular Catalysis B: Enzymatic 2007, 44 (1) , 1-7.
    16. Nuria Armesto, Susana Fernández, Miguel Ferrero, Vicente Gotor. Influence of intramolecular hydrogen bonds in the enzyme-catalyzed regioselective acylation of quinic and shikimic acid derivatives. Tetrahedron 2006, 62 (23) , 5401-5410.
    17. Pablo Domínguez de María, Chiara Carboni-Oerlemans, Bernard Tuin, Gerrald Bargeman, Ab van der Meer, Robert van Gemert. Biotechnological applications of Candida antarctica lipase A: State-of-the-art. Journal of Molecular Catalysis B: Enzymatic 2005, 37 (1-6) , 36-46.

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