(3R) methyl β-hydroxy-β-(p-methoxyphenyl) propionate | 135505-14-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (3R) methyl β-hydroxy-β-(p-methoxyphenyl) propionate
• 英文别名: (R)-(+)-methyl 3-(4-methoxyphenyl)-3-hydroxypropanoate；(3R) methyl 3-hydroxy-3-(4-methoxyphenyl)propanoate；(R)-methyl 3-(4-methoxyphenyl)-3-hydroxypropanoate；(R)-methyl 3-hydroxy-3-(4-methoxyphenyl)propanoate；Methyl (R)-3-Hydroxy-3-(4-methoxyphenyl)propanoate；methyl (3R)-3-hydroxy-3-(4-methoxyphenyl)propanoate
• CAS: 135505-14-5
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: SLSMILXGFSQOHY-SNVBAGLBSA-N

物化性质

• 熔点：
  67-68 °C(Solv: benzene (71-43-2); hexane (110-54-3))
• 沸点：
  341.4±32.0 °C(Predicted)
• 密度：
  1.161±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 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：

  3-(4-甲氧基苯基)-3-羟基丙酸甲酯 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 、 magnesium chloride 、 磷脂酶B 作用下， 以 二氯甲烷 、 异丙醚 、 水 为溶剂， 反应 24.0h， 生成 (3R) methyl β-hydroxy-β-(p-methoxyphenyl) propionate
  参考文献：
  名称：

  Candida Rugosa lipase-catalyzed kinetic resolution of β-hydroxy-β-arylpropionates and δ-hydroxy-δ-aryl-β-oxo-pentanoates

  摘要：

  A simple and convenient method was reported for the preparation of optically active beta-hydroxy-beta-arylpropionates, delta-hydroxy-delta-aryl-beta-oxo-pentanoates and their butyryl derivatives via CRL-catalyzed hydrolysis. The optically active products are potential precursors of some chiral pharmaceuticals and natural products. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2004.12.059

文献信息

• Enantioselective Hydrogenation of β-Keto Esters using Chiral Diphosphine-Ruthenium Complexes: Optimization for Academic and Industrial Purposes and Synthetic Applications
  作者：V. Ratovelomanana-Vidal、C. Girard、R. Touati、J. P. Tranchier、B. Ben Hassine、J. P. Genêt

  DOI：10.1002/adsc.200390021

  日期：2003.1

  Enantioselective hydrogenation using chiral complexes between atropisomeric diphosphines and ruthenium is a powerful tool for producing chiral compounds. Using a simple and straightforward in situ catalyst preparation, the conditions were optimized using molecular hydrogen for both academic and industrial purposes. This led to the best conditions and the lowest catalytic ratio required for the pressure

  使用对映异构体二膦与钌之间的手性配合物进行对映选择性氢化是生产手性化合物的有力工具。使用简单直接的原位催化剂制备方法，出于学术和工业目的，使用分子氢对条件进行了优化。这导致所用压力所需的最佳条件和最低催化比。各种β-酮酯的氢化反应均在大气压和较高压力下有效进行，从而导致使用非常低的催化剂/底物比例，最高可达1 / 20,000。不对称氢化用于关键步骤，以合成胭脂红酸，度洛西汀和氟西汀。
• Lewis Base Activation of Lewis Acids:  Catalytic, Enantioselective Addition of Silyl Ketene Acetals to Aldehydes
  作者：Scott E. Denmark、Gregory L. Beutner、Thomas Wynn、Martin D. Eastgate

  DOI：10.1021/ja047339w

  日期：2005.3.1

  The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent

  路易斯酸的路易斯碱活化的概念已被简化用于催化甲硅烷基乙烯酮缩醛和甲硅烷基二烯醇醚与醛的羟醛反应。弱酸性物质四氯化硅 (SiCl4) 可以通过结合强路易斯碱性手性磷酰胺而被激活，导致手性路易斯酸的原位形成。该物质已被证明是将乙酸酯、丙酸酯和异丁酸酯衍生的甲硅烷基乙烯酮缩醛与共轭和非共轭醛进行羟醛加成反应的有效催化剂。此外，还证明了甲硅烷基二烯醇醚的乙烯基羟醛反应。高水平的区域-，抗非对映-，
• Iridium-catalyzed asymmetric hydrogenation of <font>β</font>-keto esters with f-amphox ligands
  作者：Chao Qin、Xiu-Shuai Chen、Chuan-Jin Hou、Hongzhu Liu、Yan-Jun Liu、De-Zhi Huang、Xiang-Ping Hu

  DOI：10.1080/00397911.2017.1414267

  日期：2018.3.19

  ABSTRACT The iridium-catalyzed asymmetric hydrogenation of β-keto esters with chiral tridentate P,N,N-ligands (f-amphox) has been developed. Under the optimized conditions, a wide range of β-keto esters can be hydrogenated smoothly, affording the corresponding β-hydroxy esters in good to excellent enantioselectivities (up to 95% ee). GRAPHICAL ABSTRACT

  摘要 铱催化β-酮酯与手性三齿P,N,N-配体(f-amphox) 的不对称氢化反应已被开发出来。在优化的条件下，多种β-酮酯可以顺利氢化，得到相应的β-羟基酯，具有良好到优异的对映选择性（高达95% ee）。图形概要
• Enantioselective Hydrogenation of β-Ketoesters Using a MeO-PEG-Supported Biphep Ligand under Atmospheric Pressure: A Practical Synthesis of (<i>S</i>)-Fluoxetine
  作者：Quanrui Wang、Liting Chai、Huansheng Chen、Zhiming Li、Fenggang Tao

  DOI：10.1055/s-2006-949650

  日期：2006.9

  The preparation of a novel chiral 2,2′-bis(MeO-PEG-supported)-6,6′-bis(diphenylphosphanyl)biphenyl (MeO-PEG-Biphep) ligand is described. The derived ruthenium complex catalyzes the hydrogenation of β-ketoesters in up to 99% yield and 99% ee under atmospheric pressure. The accelerating effects exerted by the PEG linkage are dramatic when compared to the unsupported analogue, MeO-Biphep-RuBr2. Furthermore, the catalyst can be recovered easily and the recycled catalysts were shown to maintain their efficiency in two consecutive runs, albeit with declining activity. One of the products, (S)-ethyl-3-hydroxy-3-phenylpropanoate, is useful in the preparation of (S)-fluoxetine.

  报道了一种新型手性2,2′-双(甲氧基-PEG-支撑)-6,6′-双(二苯基膦)联苯(MeO-PEG-Biphep)配体的制备。由此衍生的钌配合物在大气压下催化β-酮酯的氢化反应，产率高达99%，对映选择性高达99% ee。与未支撑的类似物MeO-Biphep-RuBr2相比，PEG连接的加速效应显著。此外，该催化剂易于回收，回收的催化剂在连续两次运行中保持其效率，尽管活性有所下降。其中一个产物(S)-乙基-3-羟基-3-苯基丙酸酯在制备(S)-氟西汀中具有应用价值。
• Asymmetric Reduction of Aromatic Ketones. II. An Enantioselective Synthesis of Methyl(2R,3S)-3-(4-Methoxypehnyl)glycidate.
  作者：Kenji MATSUKI、Masao SOBUKAWA、Akiyoshi KAWAI、Hirozumi INOUE、Mikio TAKEDA

  DOI：10.1248/cpb.41.643

  日期：——

  Asymmetric reduction of some 3-keto esters (6, 8, and 11) to 3-hydroxy esters (7, 9, and 12) with various chiral reducing agents was investigated. The products (9 and 12) were converted to methyl (2R, 3S)-3-(4-methoxy-phenyl)glycidate (2R, 3S-3), a key intermediate in the practical enantioselective synthesis of dilitazem (1).

  研究了某些3-酮酯（6、8和11）通过不同手性还原剂不对称还原为3-羟基酯（7、9和12）的过程。产物（9和12）被转化为甲基（2R, 3S）-3-（4-甲氧基苯基）缩水甘油酸酯（2R, 3S-3），这是在实际合成Diltiazem（1）的对映选择性合成中的关键中间体。