2-diazo-5-(2'-methoxyphenyl)-6-methylheptan-3-one | 378233-78-4

• 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: 2-diazo-5-(2'-methoxyphenyl)-6-methylheptan-3-one
• 英文别名: 2-Diazo-5-(2-methoxyphenyl)-6-methylheptan-3-one；2-diazo-5-(2-methoxyphenyl)-6-methylheptan-3-one
• CAS: 378233-78-4
• 化学式: C₁₅H₂₀N₂O₂
• 分子量: 260.336
• InChiKey: GMQUWCSJJRIXNT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-diazo-5-(2'-methoxyphenyl)-6-methylheptan-3-one 在 rhodium(II) acetate dimer 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 cis-(3R*,8aR*)-3,8a-dihydro-3-isopropyl-8-methoxy-8a-methylazulen-1(2H)-one 、 trans-(3R*,8aS*)-3,8a-dihydro-3-isopropyl-4-methoxy-8a-methylazulen-1(2H)-one
  参考文献：
  名称：

  Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents

  摘要：

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.

  DOI：

  10.1021/jo015750l
• 作为产物：
  描述：

  2-甲氧基肉桂酸 在 草酰氯 、 碘 、 magnesium 作用下， 以 乙醚 为溶剂， 反应 5.0h， 生成 2-diazo-5-(2'-methoxyphenyl)-6-methylheptan-3-one
  参考文献：
  名称：

  Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents

  摘要：

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.

  DOI：

  10.1021/jo015750l

文献信息

• Dynamic Equilibria in the Products of Intramolecular Buchner Additions of Diazoketones to Aryl Rings Bearing Methoxy Substituents
  作者：Anita R. Maguire、Patrick O'Leary、Francis Harrington、Simon E. Lawrence、Alexander J. Blake

  DOI：10.1021/jo015750l

  日期：2001.10.1

  Rhodium carboxylate catalyzed aromatic addition reactions of a range of diazoketones bearing methoxy-substituted aryl rings have been explored. While the existence of norcaradiene-cycloheptatriene equilibria in related compounds is well established, the aromatic addition products in this study display more complex dynamic equilibria due to conjugation with the methoxy group; the experimental evidence for this is discussed in detail. In the azulenone products 21-26 derived from p-methoxy-substituted diazoketones 14-16, the diastereomers interconvert via a spiro intermediate 39. A related mechanistic process in the azulenones 43-46 derived from the o-methoxy-substituted diazoketones 17, 18 interconverts regioisomers, explaining the conflicting reports for the regioselectivity of the cyclization of diazoketone 1. With the m-methoxy-substituted diazoketone 19, involvement of the methoxy group through a different pathway results in fragmentation of the azulenone to form the tetralone 47. With the azulenones 21-26 exclusive trapping of the norcaradiene associated with the less thermodynamically stable diastereomers in a cycloadduct with N-phenylmaleimide is observed. Due to the presence of the activating methoxy substituent on the aromatic ring, the aromatic addition reactions of the diazoketones studied were not very sensitive to the nature of the rhodium catalyst.