Catalytic Chemoselective O-Phosphorylation of Alcohols

K. Domon, M. Puripat, K. Fujiyoshi, M. Hatanaka, S. A. Kawashima, K. Yamatsugu, M. Kanai

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)283-292
Number of pages10
JournalACS Central Science
Volume6
Issue number2
DOIs
Publication statusPublished - 2020 Feb 26
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

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    Domon, K., Puripat, M., Fujiyoshi, K., Hatanaka, M., Kawashima, S. A., Yamatsugu, K., & Kanai, M. (2020). Catalytic Chemoselective O-Phosphorylation of Alcohols. ACS Central Science, 6(2), 283-292. https://doi.org/10.1021/acscentsci.9b01272