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In Situ Acetaldehyde Synthesis for Carboligation Reactions

The enzyme 4‐oxalocrotonate tautomerase (4‐OT) can promiscuously catalyze various carboligation reactions using acetaldehyde as a nucleophile. However, the highly reactive nature of acetaldehyde requires intricate handling, which can impede its usage in practical synthesis. Therefore, we investigate...

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Detalles Bibliográficos
Autores principales: Biewenga, Lieuwe, Kunzendorf, Andreas, Poelarends, Gerrit J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318290/
https://www.ncbi.nlm.nih.gov/pubmed/31868962
http://dx.doi.org/10.1002/cbic.201900666
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author Biewenga, Lieuwe
Kunzendorf, Andreas
Poelarends, Gerrit J.
author_facet Biewenga, Lieuwe
Kunzendorf, Andreas
Poelarends, Gerrit J.
author_sort Biewenga, Lieuwe
collection PubMed
description The enzyme 4‐oxalocrotonate tautomerase (4‐OT) can promiscuously catalyze various carboligation reactions using acetaldehyde as a nucleophile. However, the highly reactive nature of acetaldehyde requires intricate handling, which can impede its usage in practical synthesis. Therefore, we investigated three enzymatic routes to synthesize acetaldehyde in situ in one‐pot cascade reactions with 4‐OT. Two routes afforded practical acetaldehyde concentrations, using an environmental pollutant, trans‐3‐chloroacrylic acid, or a bio‐renewable, ethanol, as starting substrate. These routes can be combined with 4‐OT catalyzed Michael‐type additions and aldol condensations in one pot. This modular systems biocatalysis methodology provides a stepping stone towards the development of larger artificial metabolic networks for the practical synthesis of important chemical synthons.
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spelling pubmed-73182902020-06-29 In Situ Acetaldehyde Synthesis for Carboligation Reactions Biewenga, Lieuwe Kunzendorf, Andreas Poelarends, Gerrit J. Chembiochem Full Papers The enzyme 4‐oxalocrotonate tautomerase (4‐OT) can promiscuously catalyze various carboligation reactions using acetaldehyde as a nucleophile. However, the highly reactive nature of acetaldehyde requires intricate handling, which can impede its usage in practical synthesis. Therefore, we investigated three enzymatic routes to synthesize acetaldehyde in situ in one‐pot cascade reactions with 4‐OT. Two routes afforded practical acetaldehyde concentrations, using an environmental pollutant, trans‐3‐chloroacrylic acid, or a bio‐renewable, ethanol, as starting substrate. These routes can be combined with 4‐OT catalyzed Michael‐type additions and aldol condensations in one pot. This modular systems biocatalysis methodology provides a stepping stone towards the development of larger artificial metabolic networks for the practical synthesis of important chemical synthons. John Wiley and Sons Inc. 2020-02-12 2020-05-15 /pmc/articles/PMC7318290/ /pubmed/31868962 http://dx.doi.org/10.1002/cbic.201900666 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
Biewenga, Lieuwe
Kunzendorf, Andreas
Poelarends, Gerrit J.
In Situ Acetaldehyde Synthesis for Carboligation Reactions
title In Situ Acetaldehyde Synthesis for Carboligation Reactions
title_full In Situ Acetaldehyde Synthesis for Carboligation Reactions
title_fullStr In Situ Acetaldehyde Synthesis for Carboligation Reactions
title_full_unstemmed In Situ Acetaldehyde Synthesis for Carboligation Reactions
title_short In Situ Acetaldehyde Synthesis for Carboligation Reactions
title_sort in situ acetaldehyde synthesis for carboligation reactions
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318290/
https://www.ncbi.nlm.nih.gov/pubmed/31868962
http://dx.doi.org/10.1002/cbic.201900666
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