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Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts
Here, the streptavidin–biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8330412/ https://www.ncbi.nlm.nih.gov/pubmed/33496282 http://dx.doi.org/10.1039/d0cc08142f |
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author | Santi, Nicolò Morrill, Louis C. Świderek, Katarzyna Moliner, Vicent Luk, Louis Y. P. |
author_facet | Santi, Nicolò Morrill, Louis C. Świderek, Katarzyna Moliner, Vicent Luk, Louis Y. P. |
author_sort | Santi, Nicolò |
collection | PubMed |
description | Here, the streptavidin–biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations. |
format | Online Article Text |
id | pubmed-8330412 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-83304122021-08-09 Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts Santi, Nicolò Morrill, Louis C. Świderek, Katarzyna Moliner, Vicent Luk, Louis Y. P. Chem Commun (Camb) Chemistry Here, the streptavidin–biotin technology was applied to enable organocatalytic transfer hydrogenation. By introducing a biotin-tethered pyrrolidine (1) to the tetrameric streptavidin (T-Sav), the resulting hybrid catalyst was able to mediate hydride transfer from dihydro-benzylnicotinamide (BNAH) to α,β-unsaturated aldehydes. Hydrogenation of cinnamaldehyde and some of its aryl-substituted analogues was found to be nearly quantitative. Kinetic measurements revealed that the T-Sav:1 assembly possesses enzyme-like behavior, whereas isotope effect analysis, performed by QM/MM simulations, illustrated that the step of hydride transfer is at least partially rate-limiting. These results have proven the concept that T-Sav can be used to host secondary amine-catalyzed transfer hydrogenations. The Royal Society of Chemistry 2021-01-14 /pmc/articles/PMC8330412/ /pubmed/33496282 http://dx.doi.org/10.1039/d0cc08142f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Santi, Nicolò Morrill, Louis C. Świderek, Katarzyna Moliner, Vicent Luk, Louis Y. P. Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title | Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title_full | Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title_fullStr | Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title_full_unstemmed | Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title_short | Transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
title_sort | transfer hydrogenations catalyzed by streptavidin-hosted secondary amine organocatalysts |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8330412/ https://www.ncbi.nlm.nih.gov/pubmed/33496282 http://dx.doi.org/10.1039/d0cc08142f |
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