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In Situ Acetaldehyde Synthesis for Carboligation Reactions.

ABSTRACT: 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.

SUBMITTER: Biewenga L

PROVIDER: S-EPMC7318290 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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In Situ Acetaldehyde Synthesis for Carboligation Reactions.

Biewenga Lieuwe L Kunzendorf Andreas A Poelarends Gerrit J GJ

Chembiochem : a European journal of chemical biology 20200212 10

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 ...[more]

PMID: 31868962

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