cis-1-(4-bromophenyl)-5-(tert-butoxy)-4-methyl-4-phenyl-4,5-dihydro-1H-imidazole

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-1-(4-bromophenyl)-5-(tert-butoxy)-4-methyl-4-phenyl-4,5-dihydro-1H-imidazole
• 英文别名: (4S,5R)-3-(4-bromophenyl)-5-methyl-4-[(2-methylpropan-2-yl)oxy]-5-phenyl-4H-imidazole
• 化学式: C₂₀H₂₃BrN₂O
• 分子量: 387.319
• InChiKey: BMOKNPAIYHFCDX-AZUAARDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  24.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  4-溴苯基异腈 、 potassium tert-butylate 、 alpha-甲基苄基异腈 在 copper(l) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以21%的产率得到cis-1-(4-bromophenyl)-5-(tert-butoxy)-4-methyl-4-phenyl-4,5-dihydro-1H-imidazole
  参考文献：
  名称：

  Tandem Insertion–Cyclization Reaction of Isocyanides in the Synthesis of 1,4-Diaryl-1H-imidazoles: Presence ofN-Arylformimidate Intermediate

  摘要：

  A straightforward and high-yielding synthesis of 1,4-diaryl-1H-imidazoles is reported. 1,4-Diaryl-1H-imidazoels have been difficult to access in ambient conditions, but our method utilizes two different facets of isocyanide reactivity to achieve it. The reaction is believed to involve (1) NHC-copper-catalyzed isocyanide insertion into alcohol to form an N-arylformimidate intermediate and (2) subsequent base-promoted cycloaddition with benzyl isocyanide derivatives There is cooperation between these two processes through the deprotonation of benzyl isocyanide by KOtBu. The deprotonation gives tert-butyl alcohol and the benzyl isocyanide anion which are used for the first and second steps of the reaction, respectively. Various control and kinetic experiments were carried out to gain an in-depth understanding of the reaction mechanism and isocyanide reactivity. The reaction mechanism determined by density functional theory calculations was consistent with the experimental data and provided detailed explanations for the reactivity trends.

  DOI：

  10.1021/jo501652w

文献信息

• Tandem Insertion–Cyclization Reaction of Isocyanides in the Synthesis of 1,4-Diaryl-1<i>H</i>-imidazoles: Presence of<i>N</i>-Arylformimidate Intermediate
  作者：Benjamin Pooi、Jeongbin Lee、Kyujin Choi、Hajime Hirao、Soon Hyeok Hong

  DOI：10.1021/jo501652w

  日期：2014.10.3

  A straightforward and high-yielding synthesis of 1,4-diaryl-1H-imidazoles is reported. 1,4-Diaryl-1H-imidazoels have been difficult to access in ambient conditions, but our method utilizes two different facets of isocyanide reactivity to achieve it. The reaction is believed to involve (1) NHC-copper-catalyzed isocyanide insertion into alcohol to form an N-arylformimidate intermediate and (2) subsequent base-promoted cycloaddition with benzyl isocyanide derivatives There is cooperation between these two processes through the deprotonation of benzyl isocyanide by KOtBu. The deprotonation gives tert-butyl alcohol and the benzyl isocyanide anion which are used for the first and second steps of the reaction, respectively. Various control and kinetic experiments were carried out to gain an in-depth understanding of the reaction mechanism and isocyanide reactivity. The reaction mechanism determined by density functional theory calculations was consistent with the experimental data and provided detailed explanations for the reactivity trends.