A substrate-driven approach to determine reactivities of α,β-unsaturated carboxylic esters towards asymmetric bioreduction.
| Autor: | Tasnádi G; ACIB GmbH c/o, Biocatalytic Synthesis, University of Graz, Heinrichstrasse 28, 8010-Graz, Austria., Winkler CK, Clay D, Sultana N, Fabian WM, Hall M, Ditrich K, Faber K |
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| Jazyk: | angličtina |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2012 Aug 13; Vol. 18 (33), pp. 10362-7. Date of Electronic Publication: 2012 Jun 26. |
| DOI: | 10.1002/chem.201200990 |
| Abstrakt: | The degree of C=C bond activation in the asymmetric bioreduction of α,β-unsaturated carboxylic esters by ene-reductases was studied, and general recommendations to render these "borderline-substrates" more reactive towards enzymatic reduction are proposed. The concept of "supported substrate activation" was developed. In general, an additional α-halogenated substituent proved to be beneficial for enzymatic activity, whereas β-alkyl or β-aryl substituents were detrimental for the reactivity of nonhalogenated substrates, and α-cyano groups showed little effect. The alcohol moiety of the ester functionality was found to have a strong influence on the reaction rate. Overall, activities were determined by both steric and electronic effects. (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.) |
| Databáze: | MEDLINE |
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