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Catalytic Chemoselective O-Phosphorylation of Alcohols

[Image: see text] Phosphorylation of alcohols is a fundamentally important reaction in both life science and physical science. Product phosphate monoesters play key roles in living organisms, natural products, pharmaceuticals, and organic materials. Most of the chemical methods to date for synthesiz...

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Autores principales: Domon, K., Puripat, M., Fujiyoshi, K., Hatanaka, M., Kawashima, S. A., Yamatsugu, K., Kanai, M.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047436/
https://www.ncbi.nlm.nih.gov/pubmed/32123747
http://dx.doi.org/10.1021/acscentsci.9b01272
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author Domon, K.
Puripat, M.
Fujiyoshi, K.
Hatanaka, M.
Kawashima, S. A.
Yamatsugu, K.
Kanai, M.
author_facet Domon, K.
Puripat, M.
Fujiyoshi, K.
Hatanaka, M.
Kawashima, S. A.
Yamatsugu, K.
Kanai, M.
author_sort Domon, K.
collection PubMed
description [Image: see text] Phosphorylation of alcohols is a fundamentally important reaction in both life science and physical science. Product phosphate monoesters play key roles in living organisms, natural products, pharmaceuticals, and organic materials. Most of the chemical methods to date for synthesizing phosphate monoesters, however, require multistep sequences or are limited to specific types of substrates possibly due to harsh conditions. An alternative way to enable the simple production of phosphate monoesters from highly functionalized precursor alcohols is, thus, highly desired. We report herein a catalytic phosphorylation of alcohols with high functional group tolerance using tetrabutylammonium hydrogen sulfate (TBAHS) and phosphoenolpyruvic acid monopotassium salt (PEP-K) as the catalyst and phosphoryl donor, respectively. This method enables the direct introduction of a nonprotected phosphate group to the hydroxy group of a diverse menu of alcohol substrates, including functionalized small molecules, carbohydrates, and unprotected peptides. Nuclear magnetic resonance, mass spectrometric, and density functional theory analyses suggest that an unprecedented mixed anhydride species, generated from PEP-K and TBAHS, acts as an active phosphoryl donor in this reaction. This operationally simple and chemoselective catalytic phosphorylation allows for the efficient production of densely functionalized O-phosphorylated compounds, which are useful in diverse fields including biology and medicine.
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spelling pubmed-70474362020-03-02 Catalytic Chemoselective O-Phosphorylation of Alcohols Domon, K. Puripat, M. Fujiyoshi, K. Hatanaka, M. Kawashima, S. A. Yamatsugu, K. Kanai, M. ACS Cent Sci [Image: see text] Phosphorylation of alcohols is a fundamentally important reaction in both life science and physical science. Product phosphate monoesters play key roles in living organisms, natural products, pharmaceuticals, and organic materials. Most of the chemical methods to date for synthesizing phosphate monoesters, however, require multistep sequences or are limited to specific types of substrates possibly due to harsh conditions. An alternative way to enable the simple production of phosphate monoesters from highly functionalized precursor alcohols is, thus, highly desired. We report herein a catalytic phosphorylation of alcohols with high functional group tolerance using tetrabutylammonium hydrogen sulfate (TBAHS) and phosphoenolpyruvic acid monopotassium salt (PEP-K) as the catalyst and phosphoryl donor, respectively. This method enables the direct introduction of a nonprotected phosphate group to the hydroxy group of a diverse menu of alcohol substrates, including functionalized small molecules, carbohydrates, and unprotected peptides. Nuclear magnetic resonance, mass spectrometric, and density functional theory analyses suggest that an unprecedented mixed anhydride species, generated from PEP-K and TBAHS, acts as an active phosphoryl donor in this reaction. This operationally simple and chemoselective catalytic phosphorylation allows for the efficient production of densely functionalized O-phosphorylated compounds, which are useful in diverse fields including biology and medicine. American Chemical Society 2020-01-22 2020-02-26 /pmc/articles/PMC7047436/ /pubmed/32123747 http://dx.doi.org/10.1021/acscentsci.9b01272 Text en Copyright © 2020 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Domon, K.
Puripat, M.
Fujiyoshi, K.
Hatanaka, M.
Kawashima, S. A.
Yamatsugu, K.
Kanai, M.
Catalytic Chemoselective O-Phosphorylation of Alcohols
title Catalytic Chemoselective O-Phosphorylation of Alcohols
title_full Catalytic Chemoselective O-Phosphorylation of Alcohols
title_fullStr Catalytic Chemoselective O-Phosphorylation of Alcohols
title_full_unstemmed Catalytic Chemoselective O-Phosphorylation of Alcohols
title_short Catalytic Chemoselective O-Phosphorylation of Alcohols
title_sort catalytic chemoselective o-phosphorylation of alcohols
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7047436/
https://www.ncbi.nlm.nih.gov/pubmed/32123747
http://dx.doi.org/10.1021/acscentsci.9b01272
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