Asymmetric bioreduction of ketoesters derivatives by Kluyveromyces marxianus: influence of molecular structure on the conversion and enantiomeric excess
An. acad. bras. ciênc
;
89(3): 1403-1415, July-Sept. 2017. tab, graf
Article
in English
| LILACS
| ID: biblio-886744
ABSTRACT
ABSTRACT This study presents the bioreduction of six β-ketoesters by whole cells of Kluyveromyces marxianus and molecular investigation of a series of 13 β-ketoesters by hologram quantitative structure-activity relationship (HQSAR) in order to relate with conversion and enantiomeric excess of β-stereogenic-hydroxyesters obtained by the same methodology. Four of these were obtained as (R)-configuration and two (S)-configuration, among them four compounds exhibited >99% enantiomeric excess. The β-ketoesters series LUMO maps showed that the β-carbon of the ketoester scaffold are exposed to undergo nucleophilic attack, suggesting a more favorable β-carbon side to enzymatic reduction based on adopted molecular conformation at the reaction moment. The HQSAR method was performed on the β-ketoesters derivatives separating them into those provided predominantly (R)- or (S)-β-hydroxyesters. The HQSAR models for both (R)- and (S)-configuration showed high predictive capacity. The HQSAR contribution maps suggest the importance of β-ketoesters scaffold as well as the substituents attached therein to asymmetric reduction, showing a possible influence of the ester group carbonyl position on the molecular conformation in the enzyme catalytic site, exposing a β-carbon side to the bioconversion to (S)- and (R)-enantiomers.
Full text:
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Index:
LILACS (Americas)
Main subject:
Kluyveromyces
/
Esters
/
Ketones
Type of study:
Prognostic study
Language:
English
Journal:
An. acad. bras. ciênc
Journal subject:
Science
Year:
2017
Type:
Article
Affiliation country:
Brazil
Institution/Affiliation country:
Universidade Federal Fluminense/BR
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