期刊
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
卷 2014, 期 18, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejoc.201402211
关键词
Synthetic methods; Enzyme catalysis; Hydrolysis; Reaction mechanisms; Configuration determination; Hammett constant
资金
- Austrian Science Fund (FWF) [W9]
- Austrian Science Fund (FWF) [W 901] Funding Source: researchfish
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.
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