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Issue 4, 2014
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Steric vs. electronic effects in the Lactobacillus brevis ADH-catalyzed bioreduction of ketones

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Abstract

Lactobacillus brevis ADH (LBADH) is an alcohol dehydrogenase that is commonly employed to reduce alkyl or aryl ketones usually bearing a methyl, an ethyl or a chloromethyl as a small ketone substituent to the corresponding (R)-alcohols. Herein we have tested a series of 24 acetophenone derivatives differing in their size and electronic properties for their reduction employing LBADH. After plotting the relative activity against the measured substrate volumes we observed that apart from the substrate size other effects must be responsible for the activity obtained. Compared to acetophenone (100% relative activity), other small substrates such as propiophenone, α,α,α-trifluoroacetophenone, α-hydroxyacetophenone, and benzoylacetonitrile had relative activities lower than 30%, while medium-sized ketones such as α-bromo-, α,α-dichloro-, and α,α-dibromoacetophenone presented relative activities between 70% and 550%. Moreover, the comparison between the enzymatic activity and the obtained final conversions using an excess or just 2.5 equiv. of the hydrogen donor 2-propanol, denoted again deviations between them. These data supported that these hydrogen transfer (HT) transformations are mainly thermodynamically controlled. For instance, bulky α-halogenated derivatives could be quantitatively reduced by LBADH even employing 2.5 equiv. of 2-propanol independently of their kinetic values. Finally, we found good correlations between the IR absorption band of the carbonyl groups and the degrees of conversion obtained in these HT processes, making this simple method a convenient tool to predict the success of these transformations.

Graphical abstract: Steric vs. electronic effects in the Lactobacillus brevis ADH-catalyzed bioreduction of ketones

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Publication details

The article was received on 14 Oct 2013, accepted on 15 Nov 2013 and first published on 15 Nov 2013


Article type: Paper
DOI: 10.1039/C3OB42057D
Citation: Org. Biomol. Chem., 2014,12, 673-681
  • Open access: Creative Commons BY-NC license
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    Steric vs. electronic effects in the Lactobacillus brevis ADH-catalyzed bioreduction of ketones

    C. Rodríguez, W. Borzęcka, J. H. Sattler, W. Kroutil, I. Lavandera and V. Gotor, Org. Biomol. Chem., 2014, 12, 673
    DOI: 10.1039/C3OB42057D

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