(2R)-3,3,3-trifluoro-2-hydroxy-2-(2-methylindol-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: (2R)-3,3,3-trifluoro-2-hydroxy-2-(2-methylindol-3-yl)propionic acid methyl ester
• 英文别名: methyl (2R)-3,3,3-trifluoro-2-hydroxy-2-(2-methyl-1H-indol-3-yl)propanoate
• 化学式: C₁₃H₁₂F₃NO₃
• 分子量: 287.238
• InChiKey: QIOGKHBTRZZGKB-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  2-甲基吲哚 、 三氟乙酸甲酯 在 CSCS 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以83%的产率得到
  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

• 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]
• 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。
• Chiral Brønsted Acid Catalysts. Activation of Methyl 3,3,3-Trifluoropyruvate by Hydroxymethylpyridine-Containing Half-Sandwich Complexes
  作者：Daniel Carmona、Pilar Lamata、Antonio Sánchez、Pilar Pardo、Ricardo Rodríguez、Paola Ramírez、Fernando J. Lahoz、Pilar García-Orduña、Luis A. Oro

  DOI：10.1021/om5005463

  日期：2014.8.11

  The coordinated OH group in cationic complexes [eta(n)-ring)M(NOH)(Solv)][SbF6] and [(eta(n)-ring)M(NOH)(R)-P1}][SbF6](2) ((eta(n)-ring)M = (eta(5)-C5Me5)Rh, (eta(5)-C5Me5)Ir, (eta(6)-p-MeC(6)H(4)iPr)Ru; NOH = hydroxypyridine ligand; (R)-P1 = (R)-monophos) is deprotonated by Na2CO3, rendering bi- or mononuclear compounds of formulas [(eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)][SbF6](2) and [(eta(n)-ring)M(NO)(R)-P1}][SbF6], respectively. The complexes have been characterized by analytical and spectroscopic means, including the determination of the crystal structures of [((eta(n)-ring)M(kappa N-2,O-mu-O-NO}(2)[SbF6](2) (NOH = NOH-1, (eta(n)-ring)M = (eta(5)-C5Me5)Rh, 8a; (eta(6)-p-MeC(6)H(4)iPr)Ru, 8c) and [(eta(5)-C5Me5)Ir(NO)-((R)-P1}][SbF6] (NOH = (R)-NOH-2; (R)-11b) by X-ray diffractometric methods. In complexes [(eta(n)-ring)M(NOH)(P*)1[SbF6](2) (P* = chiral phosphoramidite ligand) the proton of the coordinated hydroxypyridine ligand is able to activate the carbonyl group of methyl 3,3,3-trifluoropyruvate toward the Friedel-Crafts addition of indoles. In most cases, quantitative conversion is achieved in a few minutes, at -70 degrees C, with an ee of up to 8296. NMR data support the activation of the pyruvate by interaction between its carbonyl oxygen and the OH group of the coordinated hydroxymethylpyridine. Therefore, the metallic complexes act as Lewis acid assisted Bronsted acid catalysts.