3-methyl-3,4-dihydro-1-(15)N,2-(13)C-quinazoline | 880267-13-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 3-methyl-3,4-dihydro-1-(15)N,2-(13)C-quinazoline
• 英文别名: 3-methyl-3,4-dihydro-1-15N,2-13C-quinazoline
• CAS: 880267-13-0
• 化学式: C₉H₁₀N₂
• 分子量: 148.174
• InChiKey: VAUUKUSVLIDODG-ZCIFZXMMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  11.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  15.6
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-methyl-3,4-dihydro-1-(15)N,2-(13)C-quinazoline 、 [RhCl(cyclooctene)2]2 、 三环己基膦 以 氘代四氢呋喃 为溶剂， 生成 trans-(3-methyl-1,2,3,4-tetrahydro-1-(15)NH,2-(13)C-quinazolin-2-ylidene)(PCy3)2RhCl 、 trans-N1-(3-methyl-3,4-dihydro-1-(15)N,2-(13)C-quinazoline)(PCy3)2RhCl
  参考文献：
  名称：

  Experimental and Computational Studies on the Mechanism of N-Heterocycle C−H Activation by Rh(I)

  摘要：

  Evidence is presented for a proposed mechanism of C-H activation of 3-methyl -3,4-dihydroquinazoline (1) by (PCy3)(2)RhCl. One intermediate (3), a coordination complex of 1 with (Pcy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed.

  DOI：

  10.1021/ja0576684
• 作为产物：
  描述：

  (2-methylaminomethyl)phenyl-15N-amine 、 甲酸-13C 反应 1.0h， 以33%的产率得到3-methyl-3,4-dihydro-1-(15)N,2-(13)C-quinazoline
  参考文献：
  名称：

  Experimental and Computational Studies on the Mechanism of N-Heterocycle C−H Activation by Rh(I)

  摘要：

  Evidence is presented for a proposed mechanism of C-H activation of 3-methyl -3,4-dihydroquinazoline (1) by (PCy3)(2)RhCl. One intermediate (3), a coordination complex of 1 with (Pcy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed.

  DOI：

  10.1021/ja0576684

文献信息

• Experimental and Computational Studies on the Mechanism of <i>N</i>-Heterocycle C−H Activation by Rh(I)
  作者：Sean H. Wiedemann、Jared C. Lewis、Jonathan A. Ellman、Robert G. Bergman

  DOI：10.1021/ja0576684

  日期：2006.2.1

  Evidence is presented for a proposed mechanism of C-H activation of 3-methyl -3,4-dihydroquinazoline (1) by (PCy3)(2)RhCl. One intermediate (3), a coordination complex of 1 with (Pcy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed.