diethyl [(S)-hydroxy(phenyl)methyl]phosphonate | 85166-92-3

• 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: diethyl [(S)-hydroxy(phenyl)methyl]phosphonate
• 英文别名: (S)-diethyl (α-hydroxybenzyl)phosphonate；(S)-(-)-Diethyl hydroxyphenylmethylphosphonate；(S)-diethyl (hydroxy(phenyl)methyl)phosphonate；(S)-diethyl [hydroxy(phenyl)methyl]phosphonate；diethyl (S)-α-hydroxybenzylphosphonate；(S)-diethyl hydroxy(phenyl)methylphosphonate；diethyl (S)-hydroxy-phenylmethylphosphonate；(S)-diethoxyphosphoryl(phenyl)methanol
• CAS: 85166-92-3
• 化学式: C₁₁H₁₇O₄P
• 分子量: 244.227
• InChiKey: SLNMJVMGIXUXFI-NSHDSACASA-N

物化性质

• 熔点：
  74-76 °C(Solv: acetonitrile (75-05-8))
• 沸点：
  362.0±35.0 °C(Predicted)
• 密度：
  1.180±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  diethyl [(S)-hydroxy(phenyl)methyl]phosphonate 在 盐酸 作用下， 以 1,4-二氧六环 为溶剂， 反应 72.0h， 生成 (-)-(S)-1-phenyl-1-hydroxymethylphosphonic acid
  参考文献：
  名称：

  不对称还原α-和β-酮膦酸酯的有效方法

  摘要：

  开发了一种高效且通用的方法，该方法使用衍生自硼氢化钠和1-（+）-或d-（-）-酒石酸的手性反应物不对称还原α-和β-酮膦酸酯。该方法被用于许多生物有趣对映体纯产品的制备：含2,3- epoxypropylphosphonate 11，2-羟基-3-氨基丙基膦酸14（磷酸- GABOB），磷酸-肉碱19，和其他在多克规模。

  DOI：

  10.1016/j.tet.2007.04.101
• 作为产物：
  描述：

  苯基膦酸二乙酯 在 sodium hexamethyldisilazane 、 (+)-8,8-二氯樟脑磺哑嗪 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以45%的产率得到diethyl [(S)-hydroxy(phenyl)methyl]phosphonate
  参考文献：
  名称：

  Chiral, non-racemic α-hydroxyphosphonates and phosphonic acids via stereoselective hydroxylation of diallyl benzylphosphonates

  摘要：

  Chiral, non-racemic alpha-hydroxyphosphonates have been prepared in high enantiomeric excess (96-98% ee), via stereoselective oxaziridine-mediated hydroxylation of diallyl benzylphosphonates. The enantiomeric purity and absolute configuration of the alpha-hydroxyphosphonates was established from H-1 and P-31 NMR spectroscopy of the (S)-O-methylmandelate esters. Deprotection of the diallyl alpha-hydroxyphosphonates under neutral conditions furnished the corresponding free phosphonic acids, retaining a high degree of stereochemical purity (90 to >98% ee). (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00786-3

文献信息

• Asymmetric hydrophosphonylation of aldehydes catalyzed by bifunctional chiral Al(III) complexes
  作者：Shaohua Gou、Xin Zhou、Jun Wang、Xiaohua Liu、Xiaoming Feng

  DOI：10.1016/j.tet.2008.01.022

  日期：2008.3

  effective enantioselective hydrophosphonylation of aldehydes. A variety of aromatic, heteroaromatic, condensed-ring, α,β-unsaturated, and aliphatic aldehydes were found to be suitable substrates for the reaction, and the desired α-hydroxy phosphonate were obtained in good to excellent yields (up to 99%) with moderate to good enantioselectivities (up to 87% ee) under mild conditions (at 0 °C). A possible

  一种新的手性双官能的Al（Ⅲ）配合物的BINOL衍生物，其中载有叔在BINOL的3,3'-位置-胺，已发展为醛的对映选择性有效hydrophosphonylation。发现各种芳族，杂芳族，稠环，α，β-不饱和和脂族醛是反应的合适底物，并且以良好或优异的收率（高达99％）获得了所需的α-羟基膦酸酯。在温和条件下（0°C）具有中等至良好的对映选择性（高达87％ee）。根据实验结果提出了可能的催化循环。
• Bis(oxazoline)-copper catalyzed enantioselective hydrophosphonylation of aldehydes
  作者：Tao Deng、Chun Cai

  DOI：10.1039/c4ra03269a

  日期：——

  A highly enantioselective copper-catalyzed hydrophosphonylation of aldehydes in the presence of bis(oxazoline) ligand is presented. The reaction proceeded smoothly under mild conditions. The resulting α-hydroxyphosphonates were obtained with high yields as well as enantioselectivities (up to 98% ee).

  提出了在双（恶唑啉）配体存在下醛的高度对映选择性的铜催化的羰基膦酰化。反应在温和的条件下顺利进行。以高收率和对映选择性（高达98％ee）获得所得的α-羟基膦酸酯。
• Manganese-proline derived new catalyst system for the enantioselective synthesis of α -hydroxyphosphonates and α -aminophosphonates
  作者：Hyun Lim、Vicklyn Datilus、Rania Teriak、Prianka Chohan、Parminder Kaur

  DOI：10.1016/j.tetlet.2017.02.088

  日期：2017.4

  A novel manganese/proline-derived catalyst system is reported for the stereoselective synthesis of α-hydroxyphosphonates and α-aminophosphonates. The reaction proceeded smoothly under mild reaction conditions with efficient reaction times. The resulting products were obtained with high yields and good enantioselectivities (up to 83% ee).

  报道了一种新颖的锰/脯氨酸衍生的催化剂体系，用于α-羟基膦酸酯和α-氨基膦酸酯的立体选择性合成。反应在温和的反应条件下以有效的反应时间顺利进行。得到的产物具有高收率和良好的对映选择性（高达83％ee）。
• Fe(III) catalyzed enantioselective hydrophosphonylation of aldehydes promoted by chiral camphor Schiff bases
  作者：Feng Xu、Yanpeng Liu、Jingxuan Tu、Chao Lei、Gaoqiang Li

  DOI：10.1016/j.tetasy.2015.07.004

  日期：2015.9

  Five novel chiral camphor Schiff bases were designed. Schiff base L3 showed high efficiency in Fe(III)-catalyzed asymmetric hydrophosphonylations of aldehydes, giving the corresponding products in high yields (up to 91%) along with moderate to good enantioselectivities (up to 82%).

  设计了五个新颖的手性樟脑席夫碱。Schiff碱L 3在Fe（III）催化的醛的不对称氢膦酰化反应中显示出很高的效率，从而以高收率（高达91％）提供了相应的产物，同时具有中等至良好的对映选择性（高达82％）。
• Synthesis of an unusual dinuclear chiral iron complex and its application in asymmetric hydrophosphorylation of aldehydes
  作者：Pandi Muthupandi、Govindasamy Sekar

  DOI：10.1039/c2ob25810b

  日期：——

  An unusual dinuclear chiral iron complex has been synthesized and effectively utilized in the asymmetric hydrophosphorylation of aldehydes to synthesize optically active α-hydroxy phosphonates with excellent yield and good enantioselectivity.

  合成了一种不寻常的双核手性铁复合物，并有效地用于醛的非对称氢磷酸化反应，合成了光学活性的α-羟基磷酸酯，产率优秀且对映选择性良好。