1,3,3,6-tetramethyl-2,3-dihydro-1H-quinolin-4-one | 959699-08-2

• 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: 1,3,3,6-tetramethyl-2,3-dihydro-1H-quinolin-4-one
• 英文别名: 1,3,3,6-tetramethyl-2H-quinolin-4-one
• CAS: 959699-08-2
• 化学式: C₁₃H₁₇NO
• 分子量: 203.284
• InChiKey: XLAGRCCUPSQKEP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 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：

  3-[N-(2-iodo-4-methylphenyl)-N-methylamino]-2,2-dimethylpropanal 在 tris-(dibenzylideneacetone)dipalladium(0) 、 caesium carbonate 、 三乙胺 、 tri tert-butylphosphoniumtetrafluoroborate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以98%的产率得到1,3,3,6-tetramethyl-2,3-dihydro-1H-quinolin-4-one
  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

• A Joint Experimental-Computational Comparative Study of the Pd⁰-Catalysed Reactions of Aryl Iodides and Aldehydes with N, O, and S Tethers
  作者：Daniel Solé、Francesco Mariani、Israel Fernández

  DOI：10.1002/ejoc.201500393

  日期：2015.6

  heteroatom (nitrogen, oxygen, and sulfur) on the course of the palladium-catalysed intramolecular reactions of aryl iodides and aldehydes having heteroatom-containing tethers has been explored by an extensive experimental–computational (DFT) study. Two series of substrates were considered, namely aldehydes bearing either the α-(2-iodobenzylheteroatom) or β-(2-iodophenylheteroatom) moieties. While some

  杂原子（氮、氧和硫）对钯催化的芳基碘化物和具有含杂原子系链的醛的分子内反应过程的影响已通过广泛的实验计算 (DFT) 研究进行了探索。考虑了两个系列的底物，即带有 α-(2-碘苄基杂原子) 或 β-(2-碘苯基杂原子) 部分的醛。虽然在 2-碘苄基系列中从氮变为氧或硫时观察到一些实验差异，但杂原子直接键合到芳环的醛显示出常见的化学行为，而不管杂原子的性质如何。通过计算方法研究了导致实验观察到的反应产物的不同反应途径。
• Palladium-Catalyzed Intramolecular Nucleophilic Substitution at the Alkoxycarbonyl Group
  作者：Daniel Solé、Olga Serrano

  DOI：10.1002/anie.200702176

  日期：2007.9.24
• Intramolecular Pd(0)-Catalyzed Reactions of β-(2-Iodoanilino) Carboxamides: Enolate Arylation and Nucleophilic Substitution at the Carboxamide Group
  作者：Daniel Solé、Olga Serrano

  DOI：10.1021/jo8020715

  日期：2008.12.5

  Two different reaction pathways, the enolate arylation and the acylation of the aryl halide, can be promoted by a Pd(0) catalyst starting from beta-(2-iodoanilino) carboxamides. The intramolecular acylation of beta-(2-iodoanilino) carboxamides reported here is the first example of a nucleophilic attack of a sigma-arylpalladium species at the carboxamide group, a framework that is usually inert toward organopalladium reagents.
• 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.