Abstract
The substrate scope of inverting alkylsulfatase Pisa1 was extended towards benzylic sec-sulfate esters by suppression of competing non-enzymatic autohydrolysis by addition of dimethyl sulfoxide as co-solvent. Detailed investigation of the mechanism of autohydrolysis in 18O-labeled buffer by using an enantiopure sec-benzylic sulfate ester as substrate revealed that from the three possible pathways (i) inverting SN2-type nucleophilic attack of [OH–] at the benzylic carbon represents the major pathway, whereas (ii) SN1-type formation of a planar benzylic carbenium ion leading to racemization was a minor event, and (iii) Retaining SN2-type nucleophilic attack at sulfur took place at the limits of detection. The data obtained are interpreted by analysis of Hammett constants of meta substituents.
Original language | English |
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Pages (from-to) | 3930-3934 |
Journal | European Journal of Organic Chemistry |
Volume | 2014 |
Issue number | 18 |
DOIs | |
Publication status | Published - 2014 |
Fields of Expertise
- Human- & Biotechnology
Treatment code (Nähere Zuordnung)
- Basic - Fundamental (Grundlagenforschung)