methyl 3,3,3-trifluoro-2-hydroxy-2-(1-methyl-1H-indol-3-yl)-propanoate | 849114-63-2

• 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: methyl 3,3,3-trifluoro-2-hydroxy-2-(1-methyl-1H-indol-3-yl)-propanoate
• 英文别名: methyl (2S)-3,3,3-trifluoro-2-hydroxy-2-(1-methylindol-3-yl)propanoate
• CAS: 849114-63-2
• 化学式: C₁₃H₁₂F₃NO₃
• 分子量: 287.238
• InChiKey: LHAJLOFSQCXZLO-LBPRGKRZSA-N

物化性质

• 沸点：
  423.4±45.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 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：
  51.5
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  1-甲基吲哚 、 三氟丙酮酸甲酯 在 3CF₃O₃S^(1-)*C₂₀H₂₀N₂*Yb⁽³⁺⁾ 作用下， 以 二氯甲烷 为溶剂， 反应 74.0h， 生成 methyl 3,3,3-trifluoro-2-hydroxy-2-(1-methyl-1H-indol-3-yl)-propanoate 、 methyl 3,3,3-trifluoro-2-hydroxy-2-(1-methyl-1H-indol-3-yl)-propanoate
  参考文献：
  名称：

  Enantioselective Friedel–Crafts alkylation of indole derivatives catalyzed by new Yb(OTf)₃-pyridylalkylamine complexes as chiral Lewis acids

  摘要：

  新型的Yb(OTf)3-吡啶基烷基胺配合物已被用作手性Lewis酸，在三氟丙酮酸存在下进行吲哚衍生物的非对映选择性Friedel-Crafts烷基化反应。我们研究了取代基及配体构型的影响，并实现了高达83%的对映体过量。

  DOI：

  10.1039/c0ob00461h

文献信息

• Enantioselective Friedel–Crafts alkylation of indole derivatives catalyzed by new Yb(OTf)₃-pyridylalkylamine complexes as chiral Lewis acids
  作者：Guillaume Grach、Aurelia Dinut、Sylvain Marque、Jérôme Marrot、Richard Gil、Damien Prim

  DOI：10.1039/c0ob00461h

  日期：——

  New Yb(OTf)3-pyridylalkylamine complexes have been employed as chiral Lewis acids in the enantioselective Friedel–Crafts alkylation of indole derivatives with trifluoropyruvates. The influence of the substituents as well as the configuration of the ligands have been studied and allowed us to reach enantiomeric excesses up to 83%.

  新型的Yb(OTf)3-吡啶基烷基胺配合物已被用作手性Lewis酸，在三氟丙酮酸存在下进行吲哚衍生物的非对映选择性Friedel-Crafts烷基化反应。我们研究了取代基及配体构型的影响，并实现了高达83%的对映体过量。
• 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。
• 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.