10-(3,5-dimethyl-4-nitrophenyl)benzo[h]quinoline

• 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: 10-(3,5-dimethyl-4-nitrophenyl)benzo[h]quinoline
• 英文别名: 10-(3,5-Dimethyl-4-nitrophenyl)benzo[h]quinoline
• 化学式: C₂₁H₁₆N₂O₂
• 分子量: 328.37
• InChiKey: DIKFAOWBQXMXRV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  58.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  palladium benzo[h]quinolyl acetate dimer 、 2,6-二甲基硝基苯 在 二甲基亚砜 、 对苯醌 作用下， 反应 15.0h， 以100%的产率得到10-(3,5-dimethyl-4-nitrophenyl)benzo[h]quinoline
  参考文献：
  名称：

  Controlling Site Selectivity in Pd-Catalyzed Oxidative Cross-Coupling Reactions

  摘要：

  This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl -H) with cyclometalating substrates (L similar to C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.

  DOI：

  10.1021/ja1097918

文献信息

• Catalytic and Highly Regioselective Cross-Coupling of Aromatic C−H Substrates
  作者：Kami L. Hull、Melanie S. Sanford

  DOI：10.1021/ja074395z

  日期：2007.10.1

  This communication describes a new Pd-catalyzed reaction for the highly chemo- and regioselective oxidative cross-coupling of aromatic C-H bonds. This transformation is proposed to proceed via two discrete C-H activation steps whose selectivities are predominantly controlled by proximity to a ligand (first C-H activation) or by the steric environment around the arene C-H bond (second C-H activation). Furthermore, the selectivity of the second C-H activation reaction can be controlled by tuning the ligand environment around the Pd center.
• Mechanism of Benzoquinone-Promoted Palladium-Catalyzed Oxidative Cross-Coupling Reactions
  作者：Kami L. Hull、Melanie S. Sanford

  DOI：10.1021/ja901952h

  日期：2009.7.22

  This communication describes mechanistic studies of the Pd-catalyzed oxidative cross-coupling of benzo[h]quinoline with simple arenes. Through a series of experiments, including determination of the order of the reaction in various reagents, H/D exchange studies, kinetic isotope effect investigations, and the evaluation of electronic effects, we propose a detailed mechanism for these reactions. Importantly, this mechanism explains the key role of benzoquinone in these transformations; in addition, it provides insights that allow the rational tuning of reaction conditions to control the chemoselectivity of Ar-Ar' coupling.
• Controlling Site Selectivity in Pd-Catalyzed Oxidative Cross-Coupling Reactions
  作者：Thomas W. Lyons、Kami L. Hull、Melanie S. Sanford

  DOI：10.1021/ja1097918

  日期：2011.3.30

  This paper presents a detailed investigation of the factors controlling site selectivity in the Pd-mediated oxidative coupling of 1,3-disubstituted and 1,2,3-trisubstituted arenes (aryl -H) with cyclometalating substrates (L similar to C-H). The influence of both the concentration and the steric/electronic properties of the quinone promoter are studied in detail. In addition, the effect of steric/electronic modulation of the carboxylate ligand is discussed. Finally, we demonstrate that substitution of the carboxylate for a carbonate X-type ligand leads to a complete reversal in site selectivity for many arene substrates. The origins of these trends in site selectivity are discussed in the context of the mechanism of Pd-catalyzed oxidative cross-coupling.