(6R,7R/6S,7S)-4-methoxy-6,7-diphenyl-1,3,6,7-tetrahydro-2H-azepin-2-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (6R,7R/6S,7S)-4-methoxy-6,7-diphenyl-1,3,6,7-tetrahydro-2H-azepin-2-one
• 英文别名: (2S,3R)-5-methoxy-2,3-diphenyl-1,2,3,6-tetrahydroazepin-7-one
• 化学式: C₁₉H₁₉NO₂
• 分子量: 293.365
• InChiKey: APCXOUPCKVOBGV-IEBWSBKVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-Phenyl-2-aza-3-trimethylsilyloxy-1,3-butadiene 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 为溶剂， 反应 14.0h， 以42%的产率得到(6R,7S/6S,7R)-4-methoxy-6,7-diphenyl-1,3,6,7-tetrahydro-2H-azepin-2-one
  参考文献：
  名称：

  Fischer Carbene Complexes in Heterocyclic Synthesis. Selective Cycloaddition Reactions to 2-Aza-1,3-butadienes

  摘要：

  A structurally diverse set of Fischer carbene complexes are reacted with substituted 3-[(trimethylsilyl)oxy]-2-aza-1,3-butadienes 1, yielding 5- to 7-membered nitrogen-containing heterocycles in a selective manner. Aryl and heteroarylmetal carbenes 2 undergo [4 + 1] cycloaddition with 1 leading to pyrrolidone derivatives 3-5 or 6-9, depending on the C1-substituent of 1. The [(trimethylsilyl)ethynyl]carbene 10a gives rise to metal-containing and metal-free [4 + 2] cycloadducts 11 and 12, respectively, whereas the (phenylethynyl)carbene 10b furnishes azafluorenones 13 by a tandem [4 + 2] cycloaddition/pentaannulation process. In the case of alkenyl carbene complexes 14 the regioselective [4 + 3] cycloaddition is the only observed transformation. Thus, their reaction with the phenyl-substituted azadiene 1d-resulted in the formation of a approximate to 1:1 mixture of diastereoisomers 15 and 16, whereas in the case of the tert-butyl-substituted azadiene Ic the cis-diastereoisomers 15 are selectively formed. This heptaannulation is proposed to occur by a cyclopropanation/aza-Cope rearrangement.

  DOI：

  10.1021/jo9715074

文献信息

• Fischer Carbene Complexes in Heterocyclic Synthesis. Selective Cycloaddition Reactions to 2-Aza-1,3-butadienes
  作者：José Barluenga、Miguel Tomás、Alfredo Ballesteros、Javier Santamaría、Angel Suárez-Sobrino

  DOI：10.1021/jo9715074

  日期：1997.12.1

  A structurally diverse set of Fischer carbene complexes are reacted with substituted 3-[(trimethylsilyl)oxy]-2-aza-1,3-butadienes 1, yielding 5- to 7-membered nitrogen-containing heterocycles in a selective manner. Aryl and heteroarylmetal carbenes 2 undergo [4 + 1] cycloaddition with 1 leading to pyrrolidone derivatives 3-5 or 6-9, depending on the C1-substituent of 1. The [(trimethylsilyl)ethynyl]carbene 10a gives rise to metal-containing and metal-free [4 + 2] cycloadducts 11 and 12, respectively, whereas the (phenylethynyl)carbene 10b furnishes azafluorenones 13 by a tandem [4 + 2] cycloaddition/pentaannulation process. In the case of alkenyl carbene complexes 14 the regioselective [4 + 3] cycloaddition is the only observed transformation. Thus, their reaction with the phenyl-substituted azadiene 1d-resulted in the formation of a approximate to 1:1 mixture of diastereoisomers 15 and 16, whereas in the case of the tert-butyl-substituted azadiene Ic the cis-diastereoisomers 15 are selectively formed. This heptaannulation is proposed to occur by a cyclopropanation/aza-Cope rearrangement.