(R)-diethyl 1-hydroxypropylphosphonate | 160621-45-4

• 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: (R)-diethyl 1-hydroxypropylphosphonate
• 英文别名: (1R)-1-diethoxyphosphorylpropan-1-ol
• CAS: 160621-45-4
• 化学式: C₇H₁₇O₄P
• 分子量: 196.183
• InChiKey: AUVAYJFCWUIFDE-SSDOTTSWSA-N

物化性质

• 沸点：
  268.0±23.0 °C(Predicted)
• 密度：
  1.096±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  6
• 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：

  (R)-diethyl 1-hydroxypropylphosphonate 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 (1S)-1-azido-1-diethoxyphosphorylpropane
  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-oxopropyl)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 (S)-diethyl 1-hydroxypropylphosphonate 、 (R)-diethyl 1-hydroxypropylphosphonate
  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

• Kinetic resolution of hydroxyalkanephosphonates catalyzed by Candida antarctica lipase B in organic media
  作者：Yonghui Zhang、Chengye Yuan、Zuyi Li

  DOI：10.1016/s0040-4020(02)00229-6

  日期：2002.4

  A series of hydroxyalkanephosphonates were studied as substrates for CALB catalyzed acetylation with emphasis on enantioselectivity and chemical structure of substrates. Some hydroxyalkanephosphonates could be resolved successfully to give both (R)- and (S)-isomers with high enantiomeric excess.

  研究了一系列羟基链烷膦酸酯作为CALB催化乙酰化反应的底物，重点是底物的对映选择性和化学结构。一些羟基链烷膦酸酯可以成功地拆分，以得到具有高对映体过量的（R）-和（S）-异构体。
• Enzymatic synthesis of phosphocarnitine, phosphogabob and fosfomycinStudies on organophosphorus compounds. Part 128. For Part 127, see C. Yuan, C. Xu and Y. Zhang, Tetrahedron, 2003, 59, 6095.
  作者：Ke Wang、Yonghui Zhang、Chengye Yuan

  DOI：10.1039/b307638p

  日期：——

  Phosphocarnitine was conveniently obtained from easily available diethyl 3-chloro-2-oxopropanephosphonates, followed by subsequent reduction, Mucor miehei lipase (IM) mediated resolution, amination and dealkylation. Candida antarctica lipase B (CALB) served as an effective biocatalyst in the resolution of several 1- or 2- hydroxyalkanephosphonates. The chlorine atom in different positions on the molecules greatly affected their enantioselectivity. CALB also showed satisfactory enantioselectivity toward those molecules bearing an azido moiety. Both enantiomers of phosphogabob and fosfomycin were also prepared via CALB-mediated resolution as the key step.

  从易于获得的 3-氯-2-氧代丙烷膦酸二乙酯中方便地获得了磷卡尼汀，随后进行了还原、Mucor miehei 脂肪酶（IM）介导的解析、胺化和脱烷基化。白色念珠菌脂肪酶 B（CALB）是一种有效的生物催化剂，可用于多种 1-或 2-羟基烷基膦酸盐的分解。分子上不同位置的氯原子极大地影响了它们的对映选择性。CALB 对含有叠氮基的分子也表现出令人满意的对映选择性。磷霉素和磷霉素的两种对映体也都是通过 CALB 介导的解析作为关键步骤制备的。
• An Efficient Route to Chiral α- and β-Hydroxyalkanephosphonates
  作者：Oscar Pàmies、Jan-E. Bäckvall

  DOI：10.1021/jo026888m

  日期：2003.6.1

  Enzymatic kinetic resolution of alpha- and beta-hydroxyphosphonates in combination with ruthenium-catalyzed alcohol isomerization led to a successful dynamic kinetic resolution. A variety of racemic hydroxyphosphonates were efficiently transformed to the corresponding enantiomerically pure acetates (ee up to 99% and yield up to 87%).
• 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.
• Enantioselective synthesis of diethyl 1-hydroxyalkylphosphonates via oxazaborolidine catalyzed borane reduction of diethyl α-ketophosphonates
  作者：Tadeusz Gajda

  DOI：10.1016/s0957-4166(00)86271-0

  日期：1994.10

  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.