Catalytic Chemoselective O-Phosphorylation of Alcohols.,ACS Central Science

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Catalytic Chemoselective O-Phosphorylation of Alcohols.
ACS Central Science ( IF 12.7 ) Pub Date : 2020-01-22 , DOI: 10.1021/acscentsci.9b01272
K Domon ₁ , M Puripat ₂ , K Fujiyoshi ₁ , M Hatanaka _{2,

3} , S A Kawashima ₁ , K Yamatsugu ₁ , M Kanai ₁

Affiliation

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.

中文翻译：

醇的催化化学选择性O-磷酸化。

醇的磷酸化在生命科学和物理科学中都是至关重要的反应。产品磷酸单酯在生物，天然产物，药物和有机材料中起关键作用。迄今为止，大多数合成磷酸单酯的化学方法都需要多步操作，或者可能由于恶劣的条件而限于特定类型的底物。因此，非常需要一种能够由高度官能化的前体醇简单地生产磷酸单酯的替代方法。我们在本文中报告了分别使用硫酸四丁铵硫酸氢盐（TBAHS）和磷酸烯醇丙酮酸单钾盐（PEP-K）作为催化剂和磷酰基供体的具有高官能团耐受性的醇的催化磷酸化作用。该方法能够将未保护的磷酸基团直接引入各种醇底物菜单中的羟基，所述醇底物包括功能化的小分子，碳水化合物和未保护的肽。核磁共振，质谱和密度泛函理论分析表明，由PEP-K和TBAHS生成的前所未有的混合酸酐物质在该反应中充当了活性磷酰基供体。这种操作简单且化学选择性的催化磷酸化可有效生产密集功能化的O-磷酸化化合物，该化合物可用于包括生物学和医学在内的各种领域。和未保护的肽。核磁共振，质谱和密度泛函理论分析表明，由PEP-K和TBAHS生成的前所未有的混合酸酐物质在该反应中充当了活性磷酰基供体。这种操作简单且化学选择性的催化磷酸化可有效生产密集功能化的O-磷酸化化合物，该化合物可用于包括生物学和医学在内的各种领域。和未保护的肽。核磁共振，质谱和密度泛函理论分析表明，由PEP-K和TBAHS生成的前所未有的混合酸酐物质在该反应中充当了活性磷酰基供体。这种操作简单且化学选择性的催化磷酸化可有效生产密集功能化的O-磷酸化化合物，该化合物可用于包括生物学和医学在内的各种领域。

更新日期：2020-02-26

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