dimethyl [hydroxy(o-tolyl)methyl]phosphonate

• 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: dimethyl [hydroxy(o-tolyl)methyl]phosphonate
• 英文别名: (S)-dimethoxyphosphoryl-(2-methylphenyl)methanol
• 化学式: C₁₀H₁₅O₄P
• 分子量: 230.2
• InChiKey: OUXNYVPHBCUAAM-JTQLQIEISA-N

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：

  在 phosphate buffer 、 lipase FAP 15 (from Rhizopus oryzae) 作用下， 以 正己烷 为溶剂， 反应 53.6h， 以28%的产率得到dimethyl [hydroxy(o-tolyl)methyl]phosphonate
  参考文献：
  名称：

  Enzymes in Organic Chemistry, Part 4: Enantioselective Hydrolysis of 1-Acyloxy(aryl)methyl- and 1-Acyloxy(heteroaryl)methylphosphonates with Lipases from Aspergillus niger and Rhizopus oryzae. A Comparative Study

  摘要：

  制备了外消旋 1-乙酰氧基（芳基）甲基膦酸盐和 1-乙酰氧基（杂芳基）甲基膦酸盐 (±)-4，并通过脂肪酶 AP 6 和 FAP 15 进行了动力学解析测试。事实证明，这两种酶在应用范围、反应速率和对映体过量方面都很有用。(S)-δ-羟基膦酸盐(-)-3 是在δ-乙酰氧基膦酸盐(±)-4 的酶水解作用下生成的。脂肪酶 FAP 15 可生成对映体过量率更高的产品。1-乙酰氧基-(2-甲氧基苯基)甲基膦酸盐要么无法进行动力学解析，要么以极低的对映选择性进行皂化。

  DOI：

  10.1055/s-1996-4288

文献信息

• Generation of Chiral Phosphonium Dialkyl Phosphite as a Highly Reactive <i>P</i>-Nucleophile: Application to Asymmetric Hydrophosphonylation of Aldehydes
  作者：Daisuke Uraguchi、Takaki Ito、Takashi Ooi

  DOI：10.1021/ja810043d

  日期：2009.3.25

  The generation of chiral tetraaminophosphonium dialkyl phosphite has been detected by low-temperature NMR analysis, and its synthetic potential as a remarkably reactive P-nucleophile has been successfully demonstrated by its application to the establishment of highly efficient and enantioselective hydrophosphonylation of various aldehydes. A systematic evaluation of the organic-base-dependent generation

  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。
• 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%）。
• Synthesis, structure, and catalytic activity of titanium complexes with chiral biaryl Schiff-base ligands
  作者：Liang Chen、Ning Zhao、Qiuwen Wang、Guohua Hou、Haibin Song、Guofu Zi

  DOI：10.1016/j.ica.2013.04.008

  日期：2013.6

  A series of chiral organo-titanium complexes have been prepared from the reaction between Ti((OPr)-Pr-i)(4) and chiral biaryl Schiff-base ligands 1H(2)-12H. The steric demand of the ligand plays an important role in the formation of the titanium complexes. For example, treatment of ligand 1H(2) with 1 equiv of Ti((OPr)-Pr-i)(4) in toluene at room temperature gives, after recrystallization from a toluene solution, the chiral bis-ligated titanium complex (L1)(2)Ti (14). While under similar reaction conditions, the more bulky ligands 2H(2), 4H(2), and 6H(2) form the mono-ligated titanium complexes (L2)Ti((OPr)-Pr-i)(2) (15), (L4)Ti((OPr)-Pr-i)(2)(19), and (L6)Ti((OPr)-Pr-i)(2) (22), respectively, in good yields. The mono-ligated titanium alkoxides can be converted to bis-ligated complex via ligand redistribution reaction. For one instance, treatment of mono-ligated complex (L2)Ti((OPr)-Pr-i)(2) (15) in benzene at 60 degrees C results in the isolation of the bis-ligated complex (L2)(2)Ti (16) in 92% yield. All titanium complexes have been characterized by various spectroscopic techniques and elemental analyses. The solid-state structures of complexes 14-21, 23, 24 and 29 have further been confirmed by X-ray diffraction analyses. The titanium complexes are active catalysts for the asymmetric hydrophosphonylation of aromatic aldehydes with moderate enantioselectivities. (C) 2013 Elsevier B.V. All rights reserved.
• Enzymes in Organic Chemistry, Part 4: Enantioselective Hydrolysis of 1-Acyloxy(aryl)methyl- and 1-Acyloxy(heteroaryl)methylphosphonates with Lipases from Aspergillus niger and Rhizopus oryzae. A Comparative Study
  作者：Gerhard Eidenhammer、Friedrich Hammerschmidt

  DOI：10.1055/s-1996-4288

  日期：1996.6

  Racemic 1-acyloxy(aryl)methyl- and 1-acyloxy(heteroaryl)methylphosphonates (±)-4 are prepared and tested for kinetic resolution by lipases AP 6 and FAP 15. Both enzymes proved to be useful in terms of broadness of application, reaction rate and enantiomeric excess. In general, reaction rates are higher with lipase AP 6 than with FAP 15. (S)-α-Hydroxyphosphonates (-)-3 are formed on enzymatic hydrolysis of α-acyloxyphosphonates (±)-4. Lipase FAP 15 gives products with higher enantiomeric excesses. 1-Acetoxy-(2-methoxyphenyl)methylphosphonates are either not kinetically resolved or are saponified with very low enantioselectivity.

  制备了外消旋 1-乙酰氧基（芳基）甲基膦酸盐和 1-乙酰氧基（杂芳基）甲基膦酸盐 (±)-4，并通过脂肪酶 AP 6 和 FAP 15 进行了动力学解析测试。事实证明，这两种酶在应用范围、反应速率和对映体过量方面都很有用。(S)-δ-羟基膦酸盐(-)-3 是在δ-乙酰氧基膦酸盐(±)-4 的酶水解作用下生成的。脂肪酶 FAP 15 可生成对映体过量率更高的产品。1-乙酰氧基-(2-甲氧基苯基)甲基膦酸盐要么无法进行动力学解析，要么以极低的对映选择性进行皂化。