(S)-ethyl 3-hydroxy-3-(4-bromophenyl)propanoate

• 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)-ethyl 3-hydroxy-3-(4-bromophenyl)propanoate
• 英文别名: 3-hydroxy-3-(4'-bromophenyl)propionic acid ethyl ester；ethyl (3S)-3-(4-bromophenyl)-3-hydroxypropanoate；(S)-ethyl 3-(4-bromophenyl)-3-hydroxypropanoate；ethyl 3-hydroxy-3-(4-bromophenyl)propanoate；ethyl 3-(4-bromophenyl)-3-hydroxypropanoate
• 化学式: C₁₁H₁₃BrO₃
• 分子量: 273.126
• InChiKey: AMCGFHIZMJGGHD-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 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：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (4-溴苯甲酰)乙酸乙酯 在 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 （R）-（+）-7-双（3,5-二叔丁基苯基）膦基7''-[（3-甲基吡啶-2-基甲基）氨基]-2,2''，3,3''-四氢-1,1''-螺双茚满 、 potassium tert-butylate 、 氢气 作用下， 以 乙醇 为溶剂， 25.0~30.0 ℃ 、810.65 kPa 条件下， 反应 0.8h， 以96%的产率得到(S)-ethyl 3-hydroxy-3-(4-bromophenyl)propanoate
  参考文献：
  名称：

  带有螺吡啶-氨基膦配体的手性铱催化剂可实现β-芳基β-酮酸酯的高效不对称加氢

  摘要：

  吨吨：带有配体1的手性铱催化剂对于β-取代的β-酮酸酯的不对称氢化非常有效。β-羟基酯产品以高收率提供，具有出色的对映选择性和高周转率（TONs）。cod = 1,5-环辛二烯。

  DOI：

  10.1002/anie.201105780

文献信息

• PROCESS OF PREPARING OPTICALLY ACTIVE B-HYDROXYCARBOXYLIC ACID DERIVATIVE
  申请人：IMAMOTO Tsuneo

  公开号：US20090030231A1

  公开（公告）日：2009-01-29

  Disclosed is a process of preparing an optically active β-hydroxycarboxylic acid derivative comprising asymmetrically hydrogenating a β-keto compound in the presence of a catalyst comprising a transition metal complex compound having a 2,3-bis(dialkylphosphino)pyrazine derivative as a ligand. The pyrazine derivative is preferably a quinoxaline derivative, and the transition metal is preferably ruthenium. Preferred examples of the quinoxaline derivative are (S,S)-2,3-bis(tert-butylmethylphosphino)quinoxaline, (R,R)-bis(tert-butylmethylphosphino)quinoxaline, (S,S)-bis(tert-adamantylmethylphosphino)quinoxaline, and (R,R)-bis(adamantylmethylphosphino)quinoxaline.

  本文揭示了一种制备光学活性β-羟基羧酸衍生物的过程，包括在存在以2,3-双(二烷基膦基)吡唑衍生物为配体的过渡金属配合物催化剂的情况下，对β-酮化合物进行不对称氢化。吡唑衍生物最好是喹啉衍生物，过渡金属最好是钌。喹啉衍生物的首选示例包括(S,S)-2,3-双(叔丁基甲基膦基)喹啉、(R,R)-双(叔丁基甲基膦基)喹啉、(S,S)-双(叔金刚烷基甲基膦基)喹啉和(R,R)-双(金刚烷基甲基膦基)喹啉。
• Highly enantioselective Ru-catalyzed hydrogenation of β-keto esters using electron-donating bis(trialkylphosphine) ligand-TangPhos
  作者：Chun-Jiang Wang、Haiyan Tao、Xumu Zhang

  DOI：10.1016/j.tetlet.2006.01.093

  日期：2006.3

  Highly electron-donating bis(trialkylphosphine) TangPhos and its corresponding ruthenium complexes provided high enantioselectivities for the hydrogenation of β-keto esters. Up to 99.8% and 99.5% ee have been achieved in hydrogenation of β-alkyl and β-aryl substituted β-keto esters, respectively. Asymmetric hydrogenation of ethyl 4-chloro acetoacetate in 98.2% ee is also reported.

  高度供电子的双（三烷基膦）TangPhos及其相应的钌配合物为β-酮酸酯的氢化提供了高对映选择性。在β-烷基和β-芳基取代的β-酮酯的氢化中，分别获得了高达99.8％和99.5％的ee。还报道了4-氯乙酰乙酸乙酯在98.2％ee中的不对称氢化。
• Chiral Iridium Catalysts Bearing Spiro Pyridine-Aminophosphine Ligands Enable Highly Efficient Asymmetric Hydrogenation of β-Aryl β-Ketoesters
  作者：Jian-Hua Xie、Xiao-Yan Liu、Xiao-Hui Yang、Jian-Bo Xie、Li-Xin Wang、Qi-Lin Zhou

  DOI：10.1002/anie.201105780

  日期：2012.1.2

  Tons of TONs: Chiral iridium catalysts bearing ligand 1 are highly efficient for the asymmetric hydrogenation of β‐substituted β‐ketoesters. The product β‐hydroxyesters are delivered in high yield with excellent enantioselectivities and high turnover numbers (TONs). cod= 1,5‐cyclooctadiene.

  吨吨：带有配体1的手性铱催化剂对于β-取代的β-酮酸酯的不对称氢化非常有效。β-羟基酯产品以高收率提供，具有出色的对映选择性和高周转率（TONs）。cod = 1,5-环辛二烯。
• Me2Zn mediated, tert-butylhydroperoxide promoted, catalytic enantioselective Reformatsky reaction with aldehydes
  作者：Pier Giorgio Cozzi、Fides Benfatti、Montse Guiteras Capdevila、Alessandro Mignogna

  DOI：10.1039/b805197f

  日期：——

  A practical and highly enantioselective catalytic Reformatsky reaction with aldehydes using a cheap, commercially available aminoalcohol as ligand is described.

  描述了使用便宜的可商购的氨基醇作为配体的与醛的实用且高度对映选择性的催化Reformatsky反应。
• Bisoxazolidine-Catalyzed Enantioselective Reformatsky Reaction
  作者：Christian Wolf、Max Moskowitz

  DOI：10.1021/jo200774e

  日期：2011.8.5

  A readily available chiral bisoxazolidine catalyzes the asymmetric Reformatsky reaction between ethyl iodoacetate and aldehydes. In the presence of 10 mol % of the ligand, dimethylzinc, and air, this method produces ethyl 3-hydroxy-3-(4-aryl)propanoates in high yields and in 75 to 80% ee at room temperature within 1 h. In contrast to aromatic substrates, relatively low ee’s are obtained with aliphatic

  容易获得的手性二恶唑烷催化碘代乙酸乙酯和醛之间的不对称Reformatsky反应。在存在10 mol％的配体，二甲基锌和空气的情况下，该方法在1小时内于室温下以高收率和75-80％ee生成3-羟基-3-（4-芳基）丙酸乙酯。与芳族底物相反，用脂肪族醛获得相对较低的ee。