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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...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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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. |
format | Online Article Text |
id | pubmed-7318290 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
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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