Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family

An unexpected, redox-neutral C=C bond isomerization of a γ-butyrolactone bearing an exo-methylene unit to the thermodynamically more favoured endo isomer (k(cat) = 0.076 s(−1)) catalysed by flavoproteins from the Old Yellow Enzyme family was discovered. Theoretical calculations and kinetic data supp...

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Autores principales: Durchschein, Katharina, Wallner, Silvia, Macheroux, Peter, Zangger, Klaus, Fabian, Walter M F, Faber, Kurt
Formato: Online Artículo Texto
Lenguaje:English
Publicado: WILEY-VCH Verlag 2012
Materias:
Full Papers
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3533789/
https://www.ncbi.nlm.nih.gov/pubmed/23024004
http://dx.doi.org/10.1002/cbic.201200475
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author Durchschein, Katharina
Wallner, Silvia
Macheroux, Peter
Zangger, Klaus
Fabian, Walter M F
Faber, Kurt
author_facet Durchschein, Katharina
Wallner, Silvia
Macheroux, Peter
Zangger, Klaus
Fabian, Walter M F
Faber, Kurt
author_sort Durchschein, Katharina
collection PubMed
description An unexpected, redox-neutral C=C bond isomerization of a γ-butyrolactone bearing an exo-methylene unit to the thermodynamically more favoured endo isomer (k(cat) = 0.076 s(−1)) catalysed by flavoproteins from the Old Yellow Enzyme family was discovered. Theoretical calculations and kinetic data support a mechanism through which the isomerization proceeds through FMN-mediated hydride addition onto exo-Cβ, followed by hydride abstraction from endo-Cβ′, which is in line with the well-established C=C bond bioreduction of OYEs. This new isomerase activity enriches the catalytic versatility of ene-reductases.
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spelling pubmed-35337892013-01-08 Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family Durchschein, Katharina Wallner, Silvia Macheroux, Peter Zangger, Klaus Fabian, Walter M F Faber, Kurt Chembiochem Full Papers An unexpected, redox-neutral C=C bond isomerization of a γ-butyrolactone bearing an exo-methylene unit to the thermodynamically more favoured endo isomer (k(cat) = 0.076 s(−1)) catalysed by flavoproteins from the Old Yellow Enzyme family was discovered. Theoretical calculations and kinetic data support a mechanism through which the isomerization proceeds through FMN-mediated hydride addition onto exo-Cβ, followed by hydride abstraction from endo-Cβ′, which is in line with the well-established C=C bond bioreduction of OYEs. This new isomerase activity enriches the catalytic versatility of ene-reductases. WILEY-VCH Verlag 2012-11-05 2012-09-28 /pmc/articles/PMC3533789/ /pubmed/23024004 http://dx.doi.org/10.1002/cbic.201200475 Text en Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://creativecommons.org/licenses/by/2.5/ Re-use of this article is permitted in accordance with the Creative Commons Deed, Attribution 2.5, which does not permit commercial exploitation.
spellingShingle Full Papers
Durchschein, Katharina
Wallner, Silvia
Macheroux, Peter
Zangger, Klaus
Fabian, Walter M F
Faber, Kurt
Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title_full Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title_fullStr Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title_full_unstemmed Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title_short Unusual C=C Bond Isomerization of an α,β-Unsaturated γ-Butyrolactone Catalysed by Flavoproteins from the Old Yellow Enzyme Family
title_sort unusual c=c bond isomerization of an α,β-unsaturated γ-butyrolactone catalysed by flavoproteins from the old yellow enzyme family
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3533789/
https://www.ncbi.nlm.nih.gov/pubmed/23024004
http://dx.doi.org/10.1002/cbic.201200475
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