(+/-)-(1-Hydroxy-3-methylbutyl)phosphonic acid dimethyl ester | 162681-25-6

• 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: (+/-)-(1-Hydroxy-3-methylbutyl)phosphonic acid dimethyl ester
• 英文别名: dimethyl 1-hydroxy-3-methyl-butyl phosphonate；(1-hydroxy-3-methyl-butyl)-phosphonic acid dimethyl ester；(1-Hydroxy-3-methyl-butyl)-phosphonsaeure-dimethylester；1-Dimethoxyphosphoryl-3-methylbutan-1-ol
• CAS: 162681-25-6
• 化学式: C₇H₁₇O₄P
• 分子量: 196.183
• InChiKey: FTUKQBLLYLQTDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  5
• 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：

  (+/-)-(1-Hydroxy-3-methylbutyl)phosphonic acid dimethyl ester 、 (R)-(-)-α-methoxyphenylacetyl chloride 在 吡啶 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 (1R)-dimethyl 1-<(2'R)-2'-methoxy-2'-phenylacetoxy>-3-methyl-butyl phosphonate 、 (1S)-dimethyl 1-<(2'R)-2'-methoxy-2'-phenylacetoxy>-3-methyl-butyl phosphonate
  参考文献：
  名称：

  α-羟基膦酸酯的对映体纯度和绝对构型的测定

  摘要：

  α-羟基膦酸酯的绝对构型通过O-甲基扁桃酸酯衍生物的NMR光谱法确定。O-扁桃酸酯非对映异构体的1 H和31 P NMR光谱区分开，观察到的化学位移可确定膦酸酯C-1的绝对构型。（1R）二甲基1的晶体结构- [（2'R）-2'-甲氧基-2'-苯基乙酰氧基] -3-苯基-2- ë丙烯基膦酸酯是通过X射线衍射来确定。该对映体可通过HPLC在手性文具相上分离，因此可以准确地确定羟基膦酸酯的对映体纯度。

  DOI：

  10.1016/0040-4020(95)00308-u
• 作为产物：
  描述：

  亚磷酸氢二甲酯 、 异戊醛 在 sodium methylate 作用下， 生成 (+/-)-(1-Hydroxy-3-methylbutyl)phosphonic acid dimethyl ester
  参考文献：
  名称：

  Abramow; Semenowa, Sb. Statei Obshch. Khim., 1953, p. 393,395

  摘要：

  DOI：

文献信息

• Biocatalytic Promiscuity of Lipases in Carbon‐Phosphorus Bond Formation
  作者：Dominik Koszelewski、Ryszard Ostaszewski

  DOI：10.1002/cctc.201900397

  日期：2019.5.20

  A promiscuous lipase‐catalyzed carbon‐phosphorus bond formation is presented. The developed enzymatic Pudovik‐Abramov reaction of various aromatic and aliphatic aldehydes with dialkyl phosphonates provides biologically and pharmacologically relevant α‐hydroxy phosphonates with the yields from 11 % to 85 %. The developed protocol proceeds in the presence of porcine pancreas lipase under environmentally

  提出了混杂的脂肪酶催化的碳-磷键形成。各种芳香族和脂肪族醛与二烷基膦酸酯的发达的酶促Pudovik‐Abramov反应可提供生物学上和药理学上相关的α-羟基膦酸酯，产率为11％至85％。所开发的方案在环境可持续的条件下在猪胰腺脂肪酶存在下进行。研究了包括酶来源，有机溶剂和温度在内的反应条件对反应过程的影响。制定的协议适用于多种醛，包括与合成有关的杂环糠醛和2-噻吩甲醛。
• Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis
  作者：Pola Cybulska、Yves-Marie Legrand、Alicja Babst-Kostecka、Sébastien Diliberto、Anna Leśniewicz、Erwan Oliviero、Valérie Bert、Clotilde Boulanger、Claude Grison、Tomasz K. Olszewski

  DOI：10.3390/molecules27103075

  日期：——

  A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts “Eco-MgZnOx” is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign thermal treatment of leaves rich in Zn, and

  提出了一种绿色有效的方法，通过在无溶剂条件下醛的氢膦酰化和生物源催化剂的促进来合成结构多样的α-羟基膦酸酯，称为生态催化剂“Eco-MgZnOx”。生态催化剂是由锌超富集植物拟南芥（Arabidopsishalleri）制备而成，对富含锌的叶子进行简单而良性的热处理，无需任何进一步的化学处理。通过 MP-AES、XRPD、HRTEM 和 STEM-EDX 技术对 Eco-MgZnOx 的元素组成和结构进行了表征。这些分析揭示了两种不寻常且有价值的混合锌镁氧化物和铁镁氧化物的天然丰富性。本研究中使用生态催化剂来证明它们在醛的氢膦酰化中的潜在用途，从而产生各种α-羟基膦酸酯衍生物，这些衍生物是现代化学工业的关键组成部分。进行计算化学以帮助区分混合氧化物生态催化剂的一些成分的作用。该方案的主要优点是转化率高、底物范围广、反应条件温和、最终产物易于纯化以及生态催化剂的制备简单。此外，Eco-MgZnOx-P
• Reactions of Chiral Phosphorous Acid Diamides: The Asymmetric Synthesis of Chiral .alpha.-Hydroxy Phosphonamides, Phosphonates, and Phosphonic Acids
  作者：Vincent J. Blazis、Kevin J. Koeller、Christopher D. Spilling

  DOI：10.1021/jo00109a025

  日期：1995.2

  Addition of aldehydes to the anions of chiral phosphorous acid diamides in THF solution gave a-hydroxy phosphonamides in good yield. The diastereoselectivity was strongly dependent upon the diamide used and ranged from poor to good. The phosphorous acid diamides 2a and 2b (R(1) = -(CH2)4-,R(2) = CH(2)Ph and CH(2)CMe(3), respectively) gave the best selectivity, and their reactions with a range of aldehydes were studied. Diamide 2b consistently gave good selectivities, whereas diamide 2a was only moderately selective. Aromatic, aliphatic, and unsaturated aldehydes are tolerated under the reaction conditions. The phosphonamides were hydrolyzed with aqueous HCl in dioxane to give a-hydroxy phosphonic acids. While direct methanolysis of the phosphonamides was unsuccessful, methylation of the phosphonic acids with diazomethane gave alpha-hydroxy dimethylphosphonates.
• Determination of the enantiomeric purity and absolute configuration of α-hydroxy phosphonates
  作者：James K. Kozlowski、Nigam P. Rath、Christopher D. Spilling

  DOI：10.1016/0040-4020(95)00308-u

  日期：1995.6

  The absolute configuration of α-hydroxy phosphonates was determined by NMR spectroscopy of the O-methyl mandelate ester derivatives. The O-methyl mandelate ester diastereoisomers are distinguishable by their 1H and 31P NMR spectra and the observed chemical shifts allow assignment of the absolute configuration of the phosphonate C-1. The crystal structure of (1R) dimethyl 1-[(2′R)-2′-methoxy-2′-phe

  α-羟基膦酸酯的绝对构型通过O-甲基扁桃酸酯衍生物的NMR光谱法确定。O-扁桃酸酯非对映异构体的1 H和31 P NMR光谱区分开，观察到的化学位移可确定膦酸酯C-1的绝对构型。（1R）二甲基1的晶体结构- [（2'R）-2'-甲氧基-2'-苯基乙酰氧基] -3-苯基-2- ë丙烯基膦酸酯是通过X射线衍射来确定。该对映体可通过HPLC在手性文具相上分离，因此可以准确地确定羟基膦酸酯的对映体纯度。
• Abramow; Semenowa, Sb. Statei Obshch. Khim., 1953, p. 393,395
  作者：Abramow、Semenowa

  DOI：——

  日期：——