(S)-diethyl 1-hydroxy-3-methylbutylphosphonate | 160621-44-3

• 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: (S)-diethyl 1-hydroxy-3-methylbutylphosphonate
• 英文别名: diethyl (S)-1-hydroxy-3-methylbutylphosphonate；(1S)-1-diethoxyphosphoryl-3-methylbutan-1-ol
• CAS: 160621-44-3
• 化学式: C₉H₂₁O₄P
• 分子量: 224.237
• InChiKey: KGWVUOHVWZFPTK-VIFPVBQESA-N

物化性质

• 沸点：
  296.5±23.0 °C(Predicted)
• 密度：
  1.056±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (S)-diethyl 1-hydroxy-3-methylbutylphosphonate 在 三(2-氯乙基)胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 20.0h， 生成 ((R)-1-Azido-3-methyl-butyl)-phosphonic acid diethyl ester
  参考文献：
  名称：

  Enantioselective synthesis of diethyl 1-hydroxyalkylphosphonates via oxazaborolidine catalyzed borane reduction of diethyl α-ketophosphonates

  摘要：

  Reduction of diethyl alpha-ketophosphonates 1 with borane and B-butyloxazaborolidine 2 as catalyst afforded diethyl (S)- or (R)-1-hydroxyalkylphosphonates 3a-d or 3e-f respectively in good yields and moderate to good enantiomeric excess (53-83 ee%). Respective diethyl (R)- and (S)-1-aminoalkylphosphonates 6 were obtained in a one-pot transformation, by the Mitsunobu reaction of 1-hydroxyphosphonates 3 with hydrazoic acid, and subsequent treatment of the intermediate azides 4, with triphenylphosphine, followed by hydrolysis df the iminophosphoranes 5 with water.

  DOI：

  10.1016/s0957-4166(00)86271-0
• 作为产物：
  描述：

  diethyl (1-oxo-3-methylbutyl)phosphonate 在 硼烷四氢呋喃络合物 、 (S)-tetrahydro-1-butyl-3,3-diphenyl-1H,3H-pyrrolo{2,1-c}{1,3,2}oxazaborole 作用下， 反应 2.0h， 生成 (R)-diethyl 1-hydroxy-3-methylbutylphosphonate 、 (S)-diethyl 1-hydroxy-3-methylbutylphosphonate
  参考文献：
  名称：

  Enantioselective synthesis of diethyl 1-hydroxyalkylphosphonates via oxazaborolidine catalyzed borane reduction of diethyl α-ketophosphonates

  摘要：

  Reduction of diethyl alpha-ketophosphonates 1 with borane and B-butyloxazaborolidine 2 as catalyst afforded diethyl (S)- or (R)-1-hydroxyalkylphosphonates 3a-d or 3e-f respectively in good yields and moderate to good enantiomeric excess (53-83 ee%). Respective diethyl (R)- and (S)-1-aminoalkylphosphonates 6 were obtained in a one-pot transformation, by the Mitsunobu reaction of 1-hydroxyphosphonates 3 with hydrazoic acid, and subsequent treatment of the intermediate azides 4, with triphenylphosphine, followed by hydrolysis df the iminophosphoranes 5 with water.

  DOI：

  10.1016/s0957-4166(00)86271-0

文献信息

• The Assignment of the Absolute Configuration of Diethyl Hydroxy- and Aminophosphonates by ¹H and ³¹P NMR Using Naproxen as a Reliable Chiral Derivatizing Agent
  作者：Katarzyna Błażewska、Piotr Paneth、Tadeusz Gajda

  DOI：10.1021/jo062097z

  日期：2007.2.1

  The assignment of the absolute configuration of hydroxy- and aminophosphonates by their double derivatization with commercially available naproxen is presented. The correlation between the spatial arrangement around the stereogenic carbon center and the signs of the ΔδRS allows determination of the absolute configuration of hydroxy- and aminophosphonates by simple comparison of the 1H and 31P NMR spectra

  提出了羟基膦酸酯和氨基膦酸酯的绝对构型通过与市售萘普生的双衍生作用的分配。周围的立构碳中心的空间排列和Δδ的符号之间的相关性RS通过简单比较（R）-和（S）-萘普生酯或酰胺衍生物的1 H和31 P NMR光谱，可以确定羟基和氨基膦酸酯的绝对构型。NMR研究对结构多样的萘普生酯和羟基膦酸酯和氨基膦酸酯的酰胺进行了广泛的构象分析（理论计算，低温实验），证明了可以成功使用简化的模型。
• Nonenzymatic kinetic resolution of racemic α-hydroxyalkanephosphonates with chiral copper catalyst
  作者：Yosuke Demizu、Atsushi Moriyama、Osamu Onomura

  DOI：10.1016/j.tetlet.2009.07.003

  日期：2009.9

  Kinetic resolution of alpha-hydroxyalkanephosphonates was efficiently performed by benzoylation in the presence of copper(II) triflate and (R,R)-Ph-BOX as a catalyst with excellent s value of up to 286. (C) 2009 Elsevier Ltd. All rights reserved.