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The Substrate Spectrum of the Inverting sec-Alkylsulfatase Pisa1

Authors

  • Markus Schober,

    1. Department of Chemistry, Organic & Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria, Fax: (+43)-316-380-9840; phone: (+43)-316-380-5332
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  • Tanja Knaus,

    1. Institute of Biochemistry, Graz University of Technology, Petersgasse 12, A-8010 Graz, Austria
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  • Michael Toesch,

    1. Department of Chemistry, Organic & Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria, Fax: (+43)-316-380-9840; phone: (+43)-316-380-5332
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  • Peter Macheroux,

    1. Institute of Biochemistry, Graz University of Technology, Petersgasse 12, A-8010 Graz, Austria
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  • Ulrike Wagner,

    1. Institute of Molecular Biosciences, Structural Biology, University of Graz, Humboldtstrasse 50/III, A-8010 Graz, Austria
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  • Kurt Faber

    Corresponding author
    1. Department of Chemistry, Organic & Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria, Fax: (+43)-316-380-9840; phone: (+43)-316-380-5332
    • Department of Chemistry, Organic & Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, A-8010 Graz, Austria, Fax: (+43)-316-380-9840; phone: (+43)-316-380-5332
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Abstract

The substrate spectrum of the inverting alkylsulfatase Pisa1 was investigated using a range of sec-alkyl sulfate esters bearing aromatic, olefinic and acetylenic moieties. Perfect enantioselectivities were obtained for substrates bearing groups of different size adjacent to the sulfate ester moiety. Insufficient selectivities could be doubled by using dimethyl sulfoxide (DMSO) as co-solvent. Hydrolytically unstable benzylic sulfate esters could be sufficiently stabilised by introduction of electron-withdrawing substituents. Overall, Pisa1 appears to be a very useful inverting alkylsulfatase for the deracemisation of rac-sec-alcohols via enzymatic hydrolysis of their corresponding sulfate esters, which furnishes homochiral products possessing the ‘anti-Kazlauskas’ configuration.

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