(S)-dimethyl (4-methyl)phenylhydroxymethylphosphonate | 176250-73-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-dimethyl (4-methyl)phenylhydroxymethylphosphonate
• 英文别名: (S)-dimethyl (hydroxy(p-tolyl)methyl)phosphonate；(S)-dimethyl hydroxy(p-tolyl)methylphosphonate；dimethyl [hydroxy(p-tolyl)methyl]phosphonate；dimethyl (S)-hydroxy(p-methylphenyl)methylphosphonate；(S)-dimethoxyphosphoryl-(4-methylphenyl)methanol
• CAS: 176250-73-0
• 化学式: C₁₀H₁₅O₄P
• 分子量: 230.2
• InChiKey: CXWWOURIHBVTKT-JTQLQIEISA-N

物化性质

• 沸点：
  353.0±37.0 °C(Predicted)
• 密度：
  1.210±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  对甲基苯甲醛 、 亚磷酸二甲酯 在 C₃₈H₄₈N₄P⁽¹⁺⁾*Cl^(1-) 、 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以91%的产率得到(S)-dimethyl (4-methyl)phenylhydroxymethylphosphonate
  参考文献：
  名称：

  作为高反应性 P-亲核试剂的手性亚磷酸二烷基膦的生成：在醛的不对称氢膦酰化中的应用

  摘要：

  手性四氨基鏻二烷基亚磷酸酯的生成已通过低温 NMR 分析检测到，并且其作为显着反应性 P-亲核试剂的合成潜力已通过其在建立各种醛的高效和对映选择性氢膦酰化中的应用而成功证明。对有机碱依赖性生成所需离子对及其作为 P-亲核试剂的反应性和选择性的系统评估表明，碱的阳离子共轭酸的结构是大量生成亚磷酸根阴离子的关键因素突出的亲核性和严格的立体控制。

  DOI：

  10.1021/ja810043d

文献信息

• Enantioselective synthesis of α-hydroxy phosphonates using the LaLi3tris(binaphthoxide) catalyst (LLB), prepared by an improved method
  作者：Hiroaki Sasai、Masahiro Bougauchi、Takayoshi Arai、Masakatsu Shibasaki

  DOI：10.1016/s0040-4039(97)00437-1

  日期：1997.4

  LaLi3tris(binaphthoxide) catalyst (LLB), which is prepared from LaCl3·7H2O (1 mol equiv), (R)- or (S)-BINOL dilithium salt (2.7 mol equiv), and NaO-t-Bu (0.3 mol equiv), is effective for the hydrophosphonylation of various aldehydes to give desired α-hydroxyphosphonates in up to 95% ee (88% yield). It is also noteworthy that with slow addition of the aldehydes the enantiomeric excesses of the products

  LALI 3三（binaphthoxide）催化剂（LLB），它是从制备的LaCl 3 ·7H 2 O（1摩尔当量），（- [R ）-或（小号）-BINOL二锂盐（2.7摩尔当量）和NaO-吨- Bu（0.3摩尔当量）可有效用于各种醛的氢膦酰化反应，以高达95％ee（88％收率）的方式提供所需的α-羟基膦酸酯。还值得注意的是，随着醛的缓慢添加，产物的对映体过量增加。
• Process for preparing asymmetric compound by using metal complex
  申请人：Nagase & Company, Ltd.

  公开号：US05847186A1

  公开（公告）日：1998-12-08

  A process for producing an asymmetric compound using a metal complex containing no rare earth metal element is disclosed. The process affords an optically active compound having high optical purity. Optically active binaphthol having the chemical formula ##STR1## and lithium aluminum hydride are reacted, or the optically active binaphthol, a dialkyl aluminum hydride, and a base containing an alkali metal (or a base containing alkaline earth metal) are reacted to prepare a metal complex comprising optically active binaphthol, aluminum, and alkali metal (or alkaline earth metal). This metal complex can be used as a catalyst to perform an asymmetric Michael reaction, an asymmetric phosphonylation reaction, or the like, to obtain, in a high yield, an asymmetric compound having high optical purity.

  披露了一种使用不含稀土金属元素的金属络合物生产不对称化合物的方法。该工艺提供了一种具有高光学纯度的光学活性化合物。具有化学式##STR1##的光学活性联萘酚和氢化锂铝反应，或者光学活性联萘酚、二烷基氢化铝和含有碱金属（或含有碱土金属）的碱反应，以制备包含光学活性联萘酚、铝和碱金属（或碱土金属）的金属络合物。这种金属络合物可以用作催化剂来执行不对称Michael反应、不对称磷酰化反应等，以高收率获得具有高光学纯度的不对称化合物。
• Enantioselective Hydrophosphonylation of Aldehydes Using an Aluminum Binaphthyl Schiff Base Complex as a Catalyst
  作者：Katsuji Ito、Hironori Tsutsumi、Masayuki Setoyama、Bunnai Saito、Tsutomu Katsuki

  DOI：10.1055/s-2007-984528

  日期：2007.7

  An aluminum binaphthyl Schiff base complex was found to be an efficient catalyst for enantioselective hydrophosphonylation of aldehydes. High enantioselectivities were obtained in reactions of both aromatic and aliphatic aldehydes (up to 84% and 86% ee, respectively).

  研究发现，一种铝二萘基希夫碱复合物是对映体选择性氢膦酰化醛的高效催化剂。在芳香醛和脂肪醛的反应中都获得了较高的对映选择性（ee值分别高达 84% 和 86%）。
• Asymmetric hydrogenation of α-keto phosphonates with chiral phosphine–phosphoramidite ligands
  作者：Qing Li、Chuan-Jin Hou、Yan-Jun Liu、Rui-Feng Yang、Xiang-Ping Hu

  DOI：10.1016/j.tetasy.2015.05.007

  日期：2015.7

  Rh-catalyzed asymmetric hydrogenation of challenging α-keto phosphonates has been developed. With a new chiral phosphine–phosphoramidite ligand, a wide range of α-keto phosphonates were hydrogenated to afford the corresponding (R)-α-hydroxy phosphonates with moderate to good enantioselectivities (up to 87% ee).

  已经开发出具有挑战性的α-酮膦酸酯的Rh催化不对称氢化。使用新的手性膦-亚磷酰胺配体，可将多种α-酮膦酸酯氢化，得到相应的（R）-α-羟基膦酸酯，具有中等至良好的对映选择性（最高87％ee）。
• Process for the preparation of an asymmetric compound using a metal
  申请人：Nagase and Co., Ltd.

  公开号：US06090969A1

  公开（公告）日：2000-07-18

  A process for producing an asymmetric compound using a metal complex containing no rare earth metal element is disclosed. The process affords an optically active compound having high optical purity. Optically active binaphthol having the chemical formula and lithium aluminum hydride are reacted, or the optically active binaphthol, a dialkyl aluminum hydride, and a base containing an alkali metal (or a base containing alkaline earth metal) are reacted to prepare a metal complex comprising optically active binaphthol, aluminum, and alkali metal (or alkaline earth metal). This metal complex can be used as a catalyst to perform an asymmetric Michael reaction, an asymmetric phosphonylation reaction, or the like, to obtain, in a high yield, an asymmetric compound having high optical purity.

  本发明揭示了一种使用不含稀土金属元素的金属配合物制备不对称化合物的方法。该方法可得到具有高光学纯度的光学活性化合物。可将具有化学式的光学活性双萘酚和锂铝氢化物反应，或将光学活性双萘酚、二烷基铝氢化物和含有碱金属（或含有碱土金属）的碱反应以制备包含光学活性双萘酚、铝和碱金属（或碱土金属）的金属配合物。该金属配合物可用作催化剂进行不对称Michael反应、不对称磷酰化反应等，以高产率获得高光学纯度的不对称化合物。