(2S)-3,3,3-trifluoro-2-hydroxy-2-(indol-3-yl)propionic acid methyl ester

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: (2S)-3,3,3-trifluoro-2-hydroxy-2-(indol-3-yl)propionic acid methyl ester
• 英文别名: (S)-methyl 3,3,3-trifluoro-2-hydroxy-2-(1H-indol-3-yl)-propanoate；methyl (2S)-3,3,3-trifluoro-2-hydroxy-2-(1H-indol-3-yl)propanoate；(s)-methyl 3,3,3-trifluoro-2-hydroxy-2-(1H-indol-3-yl)propanoate；methyl 3,3,3-trifluoro-2-hydroxy-2-(indol-3-yl)propionate
• 化学式: C₁₂H₁₀F₃NO₃
• 分子量: 273.212
• InChiKey: BJTUXJYJRFFZEC-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  62.3
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  吲哚 、 三氟乙酸甲酯 在 CSCS 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以97%的产率得到(2S)-3,3,3-trifluoro-2-hydroxy-2-(indol-3-yl)propionic acid methyl ester
  参考文献：
  名称：

  Enhanced efficiency of recyclable C3-symmetric cinchonine-squaramides in the asymmetric Friedel–Crafts reaction of indoles with alkyl trifluoropyruvate

  摘要：

  The highly enantioselective Friedel-Crafts reaction of indoles with trifluoropyruvate catalyzed by a C-3-symmetric cinchonine-squaramide is reported. A wide variety of trifluoromethylated indole derivatives were obtained in high yields and with excellent enantioselectivities (99% and up to > 99% ee). Moreover the C-3 catalyst can be easily recovered and was used five times. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.08.015

文献信息

• Asymmetric Friedel–Crafts Alkylation of Indoles with Trifluoromethyl Pyruvate Catalyzed by a Dinuclear Zinc Catalyst
  作者：Yuan-Zhao Hua、Jun-Wei Chen、Hua Yang、Min-Can Wang

  DOI：10.1021/acs.joc.7b02599

  日期：2018.2.2

  cooperative catalysis model has been reported for the asymmetric Friedel–Crafts (F–C) alkylation of indoles with trifluoromethyl pyruvates using Trost’s intramolecular dinuclear zinc complex as the catalyst. This dinuclear zinc catalyst was prepared in situ by reacting the chiral ligand (S,S)-L2b with 2 equiv of ZnEt2. A series of trifluoromethyl alcohol and indole-containing biological compounds were formed

  据报道，使用Trost分子内双核锌络合物作为催化剂，吲哚与三氟甲基丙酮酸酯的不对称Friedel-Crafts（FC）烷基化的双金属协同催化模型。这种双核锌催化剂通过手性配体（反应原位制备S，S - ）L2b的与2当量ZnEt的2。在温和的条件下，在10 mol％的催化剂存在下，以中等至良好的收率（高达95％）和良好的对映选择性（高达88％对映体过量（ee））形成一系列三氟甲醇和含吲哚的生物化合物。提出了一种协同过渡状态模型来解释不对称感应的起源。
• Enantioselective Friedel−Crafts Alkylation Reactions Catalyzed by a Chiral Nonracemic <i>C</i>₂-Symmetric 2,2‘-Bipyridyl Copper(II) Complex
  作者：Michael P. A. Lyle、Neil D. Draper、Peter D. Wilson

  DOI：10.1021/ol050075d

  日期：2005.3.1

  Enantioselective Friedel-Crafts alkylation reactions of a series of substituted indoles with methyl trifluoropyruvate, catalyzed by a chiral nonracemic C(2)-symmetric 2,2'-bipyridyl copper(II) triflate complex, are described. The corresponding 3,3,3-trifluoro-2-hydroxy-2-indole-3-yl-propionic acid methyl esters were formed in good yield and in high enantiomeric excess (up to 90%). This is the first

  描述了由手性非外消旋C（2）-对称2,2'-联吡啶基三氟甲磺酸铜络合物催化的一系列取代的吲哚与三氟丙酮酸甲酯的对映选择性Friedel-Crafts烷基化反应。形成的3,3,3-三氟-2-羟基-2-羟基-2-吲哚-3-基-丙酸甲酯以高收率和高对映体过量（最高达90％）形成。这是手性非外消旋2,2'-联吡啶基配体在催化和对映选择性Friedel-Crafts烷基化反应中的使用的首次报道。还提出了通过X射线晶体学对手性2,2'-联吡啶配体的氯化铜（II）配合物的结构表征。[反应：看文字]
• Enantioselective Friedel-Crafts Alkylation of Indoles, Pyrroles, and Furans with Trifluoropyruvate Catalyzed by Chiral Phosphoric Acid
  作者：Wataru Kashikura、Junji Itoh、Keiji Mori、Takahiko Akiyama

  DOI：10.1002/asia.200900481

  日期：2010.3.1

  Indoles, and pyrroles, and furans, oh my! Chiral phosphoric acid catalyzed Friedel–Crafts alkylation of indoles with 3,3,3‐trifluoropyruvate gave the corresponding adducts in excellent yields with high enantioselectivities. Electron‐deficient indoles, in particular, exhibited excellent enantioselectivities.

  吲哚，吡咯，呋喃，天哪！手性磷酸与3,3,3-三氟丙酮酸催化吲哚的Friedel-Crafts烷基化反应可得到高收率和高对映选择性的相应加合物。尤其是缺乏电子的吲哚表现出出色的对映选择性。
• Asymmetric Friedel-Crafts Reaction of Indoles with Ethyl Trifluoropyruvate Using a Copper(I)-Bisoxazolidine Catalyst
  作者：Christian Wolf、Peng Zhang

  DOI：10.1002/adsc.201000918

  日期：2011.3.28

  Bisoxazolidine 1 is an effective ligand in the copper(I)‐catalyzed Friedel–Crafts reaction of alkyl trifluoropyruvates and indoles. A range of ethyl 2‐(3′‐indolyl)‐3,3,3‐trifluoro‐2‐hydroxypropanoates was produced in up to 99% yield and 94% ee within 30 min to 4 h. The effect of temperature on conversion and enantioselectivity proved to be substrate specific and was optimized individually. Of particular

  Bisoxazolidine 1是三氟丙酮酸烷基酯和吲哚在铜（I）催化的Friedel-Crafts反应中的有效配体。在30分钟至4小时内，生产了一系列2-（3'-吲哚基）-3-3,3,3-三氟-2-羟基丙酸乙酯，收率高达99％，ee达到94％。温度对转化率和对映选择性的影响被证明是底物特异的，并进行了单独优化。特别令人感兴趣的是，该方法容许在吲哚环的各个位置存在取代基。在最佳温度下，底物在1或7位带有取代基的底物，产率在90-97％之间，ee值在90-94％之间。
• Heterogeneously Organocatalytic, Enantioselective Friedel-Crafts Alkylation of Indole with 3,3,3-Trifluoropyruvate
  作者：Pei Wang、Jinhui Ni、Yong An、Xiaojiang Chen、Weiwei Zhang、Yang Zhang、Guorong Ma

  DOI：10.3987/com-21-14566

  日期：——

  amine-squaramide catalyst was synthesized with diphenylethylenediamine as the chiral framework and successfully catalyzed the asymmetric Friedel-Crafts alkylation reaction between indole and trifluoropyruvate. A series of trifluoromethylated indole derivatives were obtained with high yield (up to 95%) and moderate to good enantioselectivity (up to 76% ee). The reaction proceeds in heterogeneous system, the catalyst

  以二苯乙二胺为手性骨架合成了双功能叔胺-方甲酰胺催化剂，并成功催化了吲哚与三氟丙酮酸之间的不对称傅-克烷基化反应。以高产率（高达 95%）和中等至良好的对映选择性（高达 76% ee）获得了一系列三氟甲基化吲哚衍生物。反应在非均相体系中进行，催化剂可通过简单过滤回收并循环使用。