Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases

Asymmetric synthesis of optically pure (S)-3-hydroxy-3-phenylpropanamide derivatives from o-, m- and p-substituted benzoylacetonitrile was achieved by two enzymatic one-pot protocols, the simultaneous and the sequential two-step linear cascade promoted by alcohol dehydrogenase (ADH) and nitrile hydr...

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Main Authors: Everton A. Tordato, Shirley A. Castilho, Humberto M. S. Milagre, Cintia D. F. Milagre
Format: Article
Language:English
Published: Taylor & Francis Group 2024-12-01
Series:Green Chemistry Letters and Reviews
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Online Access:https://www.tandfonline.com/doi/10.1080/17518253.2024.2343707
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author Everton A. Tordato
Shirley A. Castilho
Humberto M. S. Milagre
Cintia D. F. Milagre
author_facet Everton A. Tordato
Shirley A. Castilho
Humberto M. S. Milagre
Cintia D. F. Milagre
author_sort Everton A. Tordato
collection DOAJ
description Asymmetric synthesis of optically pure (S)-3-hydroxy-3-phenylpropanamide derivatives from o-, m- and p-substituted benzoylacetonitrile was achieved by two enzymatic one-pot protocols, the simultaneous and the sequential two-step linear cascade promoted by alcohol dehydrogenase (ADH) and nitrile hydratase (NHase). A set of commercially available ADHs and NHases were individually screened, followed by the investigation of the impact of the order of the biocatalyst addition and the effect of the substrate’s substituent. While NHases were able to hydrate o-, m-, and p-substituted electron withdrawing and electron donating substituents, the ADH was selective for the p-substituted ones. To overcome the absence of ADH catalytic activity towards beta-ketoamides, a less active NHase was employed, and the desired p-substituted products were obtained in high conversions (>99%) and ee (>99%) in the simultaneous and sequential cascade modes. Both strategies lead to optically pure (S)-3-hydroxy-3-phenylpropanamide p-substituted derivatives without the isolation of intermediates, minimizing the environmental impact and offering a greener approach.
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series Green Chemistry Letters and Reviews
spelling doaj-art-f51bafde9fd542e28d6b3c4a74b95bca2025-08-20T02:19:38ZengTaylor & Francis GroupGreen Chemistry Letters and Reviews1751-82531751-71922024-12-0117110.1080/17518253.2024.2343707Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratasesEverton A. Tordato0Shirley A. Castilho1Humberto M. S. Milagre2Cintia D. F. Milagre3São Paulo State University, Institute of Chemistry, Araraquara, BrazilSão Paulo State University, Institute of Chemistry, Araraquara, BrazilSão Paulo State University, Institute of Chemistry, Araraquara, BrazilSão Paulo State University, Institute of Chemistry, Araraquara, BrazilAsymmetric synthesis of optically pure (S)-3-hydroxy-3-phenylpropanamide derivatives from o-, m- and p-substituted benzoylacetonitrile was achieved by two enzymatic one-pot protocols, the simultaneous and the sequential two-step linear cascade promoted by alcohol dehydrogenase (ADH) and nitrile hydratase (NHase). A set of commercially available ADHs and NHases were individually screened, followed by the investigation of the impact of the order of the biocatalyst addition and the effect of the substrate’s substituent. While NHases were able to hydrate o-, m-, and p-substituted electron withdrawing and electron donating substituents, the ADH was selective for the p-substituted ones. To overcome the absence of ADH catalytic activity towards beta-ketoamides, a less active NHase was employed, and the desired p-substituted products were obtained in high conversions (>99%) and ee (>99%) in the simultaneous and sequential cascade modes. Both strategies lead to optically pure (S)-3-hydroxy-3-phenylpropanamide p-substituted derivatives without the isolation of intermediates, minimizing the environmental impact and offering a greener approach.https://www.tandfonline.com/doi/10.1080/17518253.2024.2343707Cascade reactionsalcohol dehydrogenaseketoreductasenitrile hydratase, biocatalysis, hydroxyamide
spellingShingle Everton A. Tordato
Shirley A. Castilho
Humberto M. S. Milagre
Cintia D. F. Milagre
Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
Green Chemistry Letters and Reviews
Cascade reactions
alcohol dehydrogenase
ketoreductase
nitrile hydratase, biocatalysis, hydroxyamide
title Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
title_full Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
title_fullStr Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
title_full_unstemmed Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
title_short Simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta-hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
title_sort simultaneous and sequential enzymatic cascades for asymmetric synthesis of chiral beta hydroxyamide derivatives promoted by alcohol dehydrogenases and nitrile hydratases
topic Cascade reactions
alcohol dehydrogenase
ketoreductase
nitrile hydratase, biocatalysis, hydroxyamide
url https://www.tandfonline.com/doi/10.1080/17518253.2024.2343707
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