diallyl (α,α-difluoromethyl)phosphonate | 171360-39-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: diallyl (α,α-difluoromethyl)phosphonate
• 英文别名: diallyl (α-α-difluoromethyl)phosphonate；3-[Difluoromethyl(prop-2-enoxy)phosphoryl]oxyprop-1-ene
• CAS: 171360-39-7
• 化学式: C₇H₁₁F₂O₃P
• 分子量: 212.133
• InChiKey: AXSDVVFIIDAHRK-UHFFFAOYSA-N

物化性质

• 沸点：
  213.6±40.0 °C(Predicted)
• 密度：
  1.162±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diallyl (α,α-difluoromethyl)phosphonate 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 3.75h， 生成 O-(1-(bis(allyloxy)phosphoryl)-8-((tert-butyldiphenylsilyl)oxy)-1,1-difluorooctan-2-yl) O-(perfluorophenyl) carbonothioate
  参考文献：
  名称：

  Rapid Entry into Biologically Relevant α,α-Difluoroalkylphosphonates Bearing Allyl Protection–Deblocking under Ru(II)/(IV)-Catalysis

  摘要：

  A convenient synthetic route to a,a-difluoroalkylphosphonates is described. Structurally diverse aldehydes are condensed with LiF2CP(O)-(OCH2CH=CH2)(2). The resultant alcohols are captured as the pentafluorophenyl thionocarbonates and efficiently deoxygenated with HSnBu3, BEt3, and O-2, and then smoothly deblocked with CpRu(IV)(pi-allyl)quinoline-2-carboxylate (1-2 mol %) in methanol as an ally! cation scavenger. These mild deprotection conditions provide access to free alpha,beta-difluoroalkylphosphonates in nearly quantitative yield. This methodology is used to rapidly construct new bis-alpha,alpha-difluoroalkyl phosphonate inhibitors of PTPIB (protein phosphotyrosine phosphatase-1B).

  DOI：

  10.1021/acs.orglett.9b03707
• 作为产物：
  描述：

  氟里昂-22 、 diallyl phosphite 在 sodium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 17.5h， 以54%的产率得到diallyl (α,α-difluoromethyl)phosphonate
  参考文献：
  名称：

  氟化氨基糖基膦酸酯的立体选择性合成†

  摘要：

  我们描述了将锂化二氟甲烷膦酸酯共轭加成到不同范围的硝化糖中，作为氟化氨基糖基膦酸酯的高立体选择性合成的便捷方法。我们的方法提供了产生具有生物学重要性的氨基糖基磷酸酯的水解稳定模拟物的机会。

  DOI：

  10.1039/c4ob02317j

文献信息

• Diallyl (Lithiodifluoromethyl)phosphonate: A New Reagent for the Introduction of the (Difluoromethylene)phosphonate Functionality
  作者：David B. Berkowitz、Darby G. Sloss

  DOI：10.1021/jo00126a073

  日期：1995.10
• Rapid Entry into Biologically Relevant α,α-Difluoroalkylphosphonates Bearing Allyl Protection–Deblocking under Ru(II)/(IV)-Catalysis
  作者：Kaushik Panigrahi、Xiang Fei、Masato Kitamura、David B. Berkowitz

  DOI：10.1021/acs.orglett.9b03707

  日期：2019.12.20

  A convenient synthetic route to a,a-difluoroalkylphosphonates is described. Structurally diverse aldehydes are condensed with LiF2CP(O)-(OCH2CH=CH2)(2). The resultant alcohols are captured as the pentafluorophenyl thionocarbonates and efficiently deoxygenated with HSnBu3, BEt3, and O-2, and then smoothly deblocked with CpRu(IV)(pi-allyl)quinoline-2-carboxylate (1-2 mol %) in methanol as an ally! cation scavenger. These mild deprotection conditions provide access to free alpha,beta-difluoroalkylphosphonates in nearly quantitative yield. This methodology is used to rapidly construct new bis-alpha,alpha-difluoroalkyl phosphonate inhibitors of PTPIB (protein phosphotyrosine phosphatase-1B).
• Stereoselective synthesis of fluorinated aminoglycosyl phosphonates
  作者：Sanne Bouwman、Romano V. A. Orru、Eelco Ruijter

  DOI：10.1039/c4ob02317j

  日期：——

  We describe the conjugate addition of lithiated difluoromethanephosphonates to a diverse range of nitroglycals as a convenient method for the highly stereoselective synthesis of fluorinated aminoglycosyl phosphonates. Our approach provides opportunities to produce hydrolytically stable mimics of biologically important aminoglycosyl phosphates.

  我们描述了将锂化二氟甲烷膦酸酯共轭加成到不同范围的硝化糖中，作为氟化氨基糖基膦酸酯的高立体选择性合成的便捷方法。我们的方法提供了产生具有生物学重要性的氨基糖基磷酸酯的水解稳定模拟物的机会。