1-acetyl-2-bromo-3-methyl-1H-indole | 58550-72-4

• 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: 1-acetyl-2-bromo-3-methyl-1H-indole
• 英文别名: 1-acetyl-2-bromo-3-methyl-indole；1-(2-bromo-3-methylindol-1-yl)ethanone
• CAS: 58550-72-4
• 化学式: C₁₁H₁₀BrNO
• 分子量: 252.11
• InChiKey: FBAKSXHNJDCGQX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  22
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-碘乙酰苯胺 在 palladium diacetate 、 N-溴代丁二酰亚胺(NBS) 、 potassium carbonate 、 lithium chloride 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 12.5h， 生成 1-acetyl-2-bromo-3-methyl-1H-indole
  参考文献：
  名称：

  Synthesis of 2,3-Disubstituted Indoles via Palladium-Catalyzed Annulation of Internal Alkynes

  摘要：

  The palladium-catalyzed coupling of 2-iodoaniline and the corresponding N-methyl, -acetyl, and -tosyl derivatives with a wide variety of internal alkynes provides 2,3-disubstituted indoles in good-to-excellent yields. The best results are obtained by employing an excess of the alkyne and a sodium or potassium acetate or carbonate base plus 1 equiv of either LiCl or n-Bu4NCl, occasionally adding 5 mol % PPh3. The yields with LiCl appear to be higher and more reproducible than those obtained with n-Bu4NCl. The process is quite general as far as the types of substituents which can be accommodated on the nitrogen of the aniline and the two ends of the alkyne triple bond. The reaction is quite regioselective, placing the aryl group of the aniline on the less sterically hindered end of the triple bond and the nitrogen moiety on the more sterically hindered end. This methodology readily affords 2-silylindoles, which can be easily protodesilylated, halogenated, or reacted with alkenes and Pd(OAc)(2) to produce 3-substituted indoles, 2-haloindoles, or 2-(1-alkenyl)indoles, respectively. The presence of alcohol groups in the alkyne seems to have a particularly strong directing effect, perhaps due to coordination with palladium. This catalytic process apparently involves arylpalladium formation, regioselective addition to the C-C triple bond of the alkyne, and subsequent intramolecular palladium displacement.

  DOI：

  10.1021/jo9803277

文献信息

• Halogenation of Indoles with Copper(II) Halides: Selective Synthesis of 2-Halo-, 3-Halo-, and 2,3-Dibromoindoles
  作者：Jin-Heng Li、Nai-Xing Wang、Shi Tang、Ye-Xiang Xie

  DOI：10.1055/s-2007-966030

  日期：——

  A simple and selective protocol for the halogenation of indoles with copper(II) bromide or chloride to synthesize 2-halo-, 3- halo-, and 2,3-dibromoindoles was developed. It was found that both base and water could be used as switches for the selectivity of the halogenation reactions. In the presence of copper(II) halide and sodium hydroxide, 3-haloindoles were obtained as the major prod- ucts, whereas

  开发了一种用溴化铜 (II) 或氯化铜卤化吲哚​​以合成 2-卤代、3-卤代和 2,3-二溴吲哚的简单且选择性的方案。发现碱和水都可以用作卤化反应选择性的开关。在卤化铜 (II) 和氢氧化钠存在的情况下，主要产物是 3-卤代吲哚，而当加入水而不是氢氧化钠时，选择性转向 2,3-二卤代吲哚。此外，在标准条件下，3-取代吲哚的 2-卤化也以中等至良好的产率成功进行。
• Larock, Richard C.; Yum, Eul Kgun, Journal of the American Chemical Society, 1991, vol. 113, # 17, p. 6689 - 6690
  作者：Larock, Richard C.、Yum, Eul Kgun

  DOI：——

  日期：——
• Synthesis of 2,3-Disubstituted Indoles via Palladium-Catalyzed Annulation of Internal Alkynes
  作者：R. C. Larock、E. K. Yum、M. D. Refvik

  DOI：10.1021/jo9803277

  日期：1998.10.1

  The palladium-catalyzed coupling of 2-iodoaniline and the corresponding N-methyl, -acetyl, and -tosyl derivatives with a wide variety of internal alkynes provides 2,3-disubstituted indoles in good-to-excellent yields. The best results are obtained by employing an excess of the alkyne and a sodium or potassium acetate or carbonate base plus 1 equiv of either LiCl or n-Bu4NCl, occasionally adding 5 mol % PPh3. The yields with LiCl appear to be higher and more reproducible than those obtained with n-Bu4NCl. The process is quite general as far as the types of substituents which can be accommodated on the nitrogen of the aniline and the two ends of the alkyne triple bond. The reaction is quite regioselective, placing the aryl group of the aniline on the less sterically hindered end of the triple bond and the nitrogen moiety on the more sterically hindered end. This methodology readily affords 2-silylindoles, which can be easily protodesilylated, halogenated, or reacted with alkenes and Pd(OAc)(2) to produce 3-substituted indoles, 2-haloindoles, or 2-(1-alkenyl)indoles, respectively. The presence of alcohol groups in the alkyne seems to have a particularly strong directing effect, perhaps due to coordination with palladium. This catalytic process apparently involves arylpalladium formation, regioselective addition to the C-C triple bond of the alkyne, and subsequent intramolecular palladium displacement.