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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...

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Autores principales: Santi, Nicolò, Morrill, Louis C., Świderek, Katarzyna, Moliner, Vicent, Luk, Louis Y. P.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
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.
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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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