| α-Hydroxy-β-keto acid rearrangement-decarboxylation: impact on thiamine diphosphate-dependent enzymatic transformations. | |
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MedLine Citation:
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PMID: 23172595 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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The thiamine diphosphate (ThDP) dependent MenD catalyzes the reaction of α-ketoglutarate with pyruvate to selectively form 4-hydroxy-5-oxohexanoic acid , which seems to be inconsistent with the assumed acyl donor role of the physiological substrate α-KG. In contrast the reaction of α-ketoglutarate with acetaldehyde gives exclusively the expected 5-hydroxy-4-oxo regioisomer . These reactions were studied by NMR and CD spectroscopy, which revealed that with pyruvate the observed regioselectivity is due to the rearrangement-decarboxylation of the initially formed α-hydroxy-β-keto acid rather than a donor-acceptor substrate role variation. Further experiments with other ThDP-dependent enzymes, YerE, SucA, and CDH, verified that this degenerate decarboxylation can be linked to the reduced enantioselectivity of acyloins often observed in ThDP-dependent enzymatic transformations. |
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Authors:
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Maryam Beigi; Sabrina Loschonsky; Patrizia Lehwald; Volker Brecht; Susana L A Andrade; Finian J Leeper; Werner Hummel; Michael Müller |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2012-11-22 |
Journal Detail:
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Title: Organic & biomolecular chemistry Volume: - ISSN: 1477-0539 ISO Abbreviation: Org. Biomol. Chem. Publication Date: 2012 Nov |
Date Detail:
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Created Date: 2012-11-22 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 101154995 Medline TA: Org Biomol Chem Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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Institute of Pharmaceutical Sciences, Albert-Ludwigs-Universität Freiburg, Albertstraße 25, 79104 Freiburg, Germany. michael.mueller@pharmazie.uni-freiburg.de. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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