1,4-dimethyl-1,2,3,4-tetrahydroquinoline-4-carboxaldehyde | 1407968-54-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 1,4-dimethyl-1,2,3,4-tetrahydroquinoline-4-carboxaldehyde
• 英文别名: 1,4-Dimethyl-2,3-dihydroquinoline-4-carbaldehyde；1,4-dimethyl-2,3-dihydroquinoline-4-carbaldehyde
• CAS: 1407968-54-0
• 化学式: C₁₂H₁₅NO
• 分子量: 189.257
• InChiKey: OTPICPUVVPCSPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  N-methyl-N-(3-methyl-3-butenyl)-2-iodoaniline 在 tris-(dibenzylideneacetone)dipalladium(0) 、 草酰氯 、 potassium tert-butylate 、 三乙胺 、 9-硼双环[3.3.1]壬烷 、 4,5-双二苯基膦-9,9-二甲基氧杂蒽 、 苯酚 作用下， 以 四氢呋喃 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 45.33h， 生成 1,4-dimethyl-1,2,3,4-tetrahydroquinoline-4-carboxaldehyde
  参考文献：
  名称：

  Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study

  摘要：

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.

  DOI：

  10.1021/jo301924e

文献信息

• Intramolecular Pd(0)-Catalyzed Reactions of (2-Iodoanilino)-aldehydes: A Joint Experimental–Computational Study
  作者：Daniel Solé、Francesco Mariani、Israel Fernández、Miguel A. Sierra

  DOI：10.1021/jo301924e

  日期：2012.11.16

  An extensive joint experimental-computational density functional theory (DFT) study has been carried out to gain insight into the factors that control the chemoselectivity (i.e., acylation vs alpha-arylation reaction) of palladium-catalyzed cyclizations of (2-iodoanilino)-aldehydes. To this end, the nature of the tethers joining the aniline nitrogen and the aldehyde moiety, different palladium precatalysts and reaction conditions (base and temperature), as well as different additives (mono- and bidendate ligands) has been explored. The adequate selection of these variables allows for the control of the selectivity of the process. Thus, (2-iodoanilino)-aldehydes generally lead to the formation of nucleophilic addition derived products when Cs2CO3/Et3N is used as base. In contrast, the use of stronger bases like (KOBu)-O-t (in the presence of PhOH) mainly forms alpha-arylation reaction products. The different reaction pathways leading to the experimentally observed reaction products have been studied by means of computational tools.