2-methyl-3-(1-methyl-1H-indol-3-yl)propanal | 596105-61-2

• 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: 2-methyl-3-(1-methyl-1H-indol-3-yl)propanal
• 英文别名: 2-Methyl-3-(1-methylindol-3-yl)propanal；2-methyl-3-(1-methylindol-3-yl)propanal
• CAS: 596105-61-2
• 化学式: C₁₃H₁₅NO
• 分子量: 201.268
• InChiKey: XPURXKVKFAHDEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 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：
  22
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-3-(1-methyl-1H-indol-3-yl)propanal 在 N-甲基吲哚酮 、 四丙基高钌酸铵 、 4 A molecular sieve 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 6.75h， 生成 3-((Z)-2,3-Dimethyl-pent-3-enyl)-1-methyl-1H-indole
  参考文献：
  名称：

  Catalytic C−H Bond Functionalization with Palladium(II):  Aerobic Oxidative Annulations of Indoles

  摘要：

  A palladium-catalyzed aerobic oxidative annulation of indoles is described. We have demonstrated that a variety of factors influence these cyclizations, and in particular the electronic nature of the pyridine ligand is crucial. It is also remarkable that these oxidative cyclizations can proceed in good yield despite background oxidative decomposition pathways, testament to the facile nature with which molecular oxygen can serve as the direct oxidant for Pd(0). We have also shown that the mechanism most likely involves initial indole palladation (formal C-H bond activation) followed by migratory insertion and beta-hydrogen elimination.

  DOI：

  10.1021/ja035054y
• 作为产物：
  描述：

  3-(1-methylindol-3-yl)propionaldehyde 在 copper dichloride 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 32.0h， 生成 2-methyl-3-(1-methyl-1H-indol-3-yl)propanal
  参考文献：
  名称：

  Catalytic C−H Bond Functionalization with Palladium(II):  Aerobic Oxidative Annulations of Indoles

  摘要：

  A palladium-catalyzed aerobic oxidative annulation of indoles is described. We have demonstrated that a variety of factors influence these cyclizations, and in particular the electronic nature of the pyridine ligand is crucial. It is also remarkable that these oxidative cyclizations can proceed in good yield despite background oxidative decomposition pathways, testament to the facile nature with which molecular oxygen can serve as the direct oxidant for Pd(0). We have also shown that the mechanism most likely involves initial indole palladation (formal C-H bond activation) followed by migratory insertion and beta-hydrogen elimination.

  DOI：

  10.1021/ja035054y

文献信息

• Organocatalytic Michael Addition of Indoles to α-Substituted Enals by Using a Diazepane Carboxylate Catalyst
  作者：Florent Larnaud、Adamo Sulpizi、Nicklas O. Häggman、Jonathan M. E. Hughes、Damien F. Dewez、James L. Gleason

  DOI：10.1002/ejoc.201700469

  日期：2017.5.10

  conjugate addition of indoles to α-substituted enals is achieved by using a diazepane carboxylate catalyst under mild conditions (20 mol-% catalyst, 20 mol-% TFA, acetonitrile, –20 °C). The low basicity and high nucleophilicity of this catalyst overcomes the limitations of allylic 1,3 strain in the intermediate iminium ions, which is normally observed with secondary-amine catalysts. Conjugate addition of

  通过在温和的条件下（20摩尔％的催化剂，20摩尔％的TFA，乙腈，–20°C）使用二氮杂环庚烷羧酸盐催化剂，将吲哚共轭添加到α-取代的烯醛中。该催化剂的低碱性和高亲核性克服了中间体亚胺离子中烯丙基1,3应变的局限性，这在仲胺催化剂中通常会观察到。证明了一系列取代的吲哚以及富含电子的芳族化合物与各种α-取代的烯类的共轭添加。
• Enantioselective Friedel–Crafts alkylations catalysed by well-defined iridium and rhodium half-sandwich complexes
  作者：Daniel Carmona、María Pilar Lamata、Antonio Sánchez、Fernando Viguri、Luis A. Oro

  DOI：10.1016/j.tetasy.2011.05.003

  日期：2011.4

  Aqua-complexes (S-M,R-C)-[C-p*M((R)-prophos)(H2O)][SbF6](2)(M = Rh 1, Ir 2) catalysed the alkylation of alpha,beta-unsaturated aldehydes with aromatics and heteroaromatics but in some cases, mixtures of products were obtained. Complexes 1 and 2 were also used to activate nitroalkenes for the Friedel-Crafts alkylation of a variety of aromatics and heteroaromatics, in particular, 1,3,5-trimethoxybenzene. For this substrate, the monoalkylated adduct was obtained in quantitative yield with enantioselectivities of up to 73% ee being achieved. The intermediate catalyst/nitroalkene was isolated and characterized and the complex catalyst/adduct was detected spectroscopically. From these data a plausible catalytic cycle is proposed. (C) 2011 Elsevier Ltd. All rights reserved.