N1,N3-bis[3,5-bis(trifluoromethyl)phenyl]-2-(9-isopropyl-9H-purin-6-yl)-5-(methoxycarbonyl)benzene-1,3-diamine | 1535484-25-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: N1,N3-bis[3,5-bis(trifluoromethyl)phenyl]-2-(9-isopropyl-9H-purin-6-yl)-5-(methoxycarbonyl)benzene-1,3-diamine
• CAS: 1535484-25-3
• 化学式: C₃₂H₂₂F₁₂N₆O₂
• 分子量: 750.547
• InChiKey: BUHJUTCACNQRKL-UHFFFAOYSA-N

物化性质

• 熔点：
  235-238 °C
• 沸点：
  612.6±65.0 °C(predicted)
• 密度：
  1.51±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  10.42
• 重原子数：
  52.0
• 可旋转键数：
  7.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  93.96
• 氢给体数：
  2.0
• 氢受体数：
  8.0

反应信息

• 作为产物：
  描述：

  3,5-bis(trifluoromethyl)phenyl azide 、 在 silver hexafluoroantimonate 、 dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以90%的产率得到N1,N3-bis[3,5-bis(trifluoromethyl)phenyl]-2-(9-isopropyl-9H-purin-6-yl)-5-(methoxycarbonyl)benzene-1,3-diamine
  参考文献：
  名称：

  Hydrogen-Bond-Assisted Controlled C–H Functionalization via Adaptive Recognition of a Purine Directing Group

  摘要：

  We have developed the Rh-catalyzed selective C-H functionalization of 6-arylpurines, in which the purine moiety directs the C-H bond activation of the aryl pendant. While the first C-H amination proceeds via the N1-chelation assistance, the subsequent second C-H bond activation takes advantage of an intramolecular hydrogen-bonding interaction between the initially formed amino group and one nitrogen atom, either N1 or N7, of the purinyl part. Isolation of a rhodacycle intermediate and the substrate variation studies suggest that N1 is the main active site for the C-H functionalization of both the first and second amination in 6-arylpurines, while N7 plays an essential role in controlling the degree of functionalization serving as an intramolecular hydrogen-bonding site in the second amination process. This pseudo-Curtin-Hammett situation was supported by density functional calculations, which suggest that the intramolecular hydrogen-bonding capability helps second amination by reducing the steric repulsion between the first installed ArNH and the directing group.

  DOI：

  10.1021/ja4118472