cis-(3S,8aS)-3-isopropyl-6-methoxy-8a-methyl-2,3-dihydroazulen-1(8aH)-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-(3S,8aS)-3-isopropyl-6-methoxy-8a-methyl-2,3-dihydroazulen-1(8aH)-one
• 英文别名: (3S,8aS)-6-methoxy-8a-methyl-3-propan-2-yl-2,3-dihydroazulen-1-one
• 化学式: C₁₅H₂₀O₂
• 分子量: 232.323
• InChiKey: KLVJPEDWELUXFB-WFASDCNBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-(4-Methoxy-phenyl)-4-methyl-pentanoyl chloride 在 rhodium(II) acetate dimer 作用下， 以 乙醚 、 乙酸乙酯 为溶剂， 反应 22.0h， 生成 cis-(3S,8aS)-3-isopropyl-6-methoxy-8a-methyl-2,3-dihydroazulen-1(8aH)-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

• Asymmetric Synthesis of <i>cis</i>-7-Methoxycalamenene via the Intramolecular Buchner Reaction of an α-Diazoketone
  作者：Paul A. McDowell、David A. Foley、Patrick O’Leary、Alan Ford、Anita R. Maguire

  DOI：10.1021/jo202499j

  日期：2012.2.17

  The asymmetric synthesis of cis-7-methoxycalamenene 1 has been accomplished using the intramolecular Buchner reaction of α-diazoketone 7 as the key step in the synthetic route. Upon reduction of the equilibrating azulenone structure 8, the resulting azulenol 9 rearranges to dihydronaphthalene 10 containing the 6,6-membered bicyclic ring system characteristic of 1, by means of an acid-catalyzed aromatization

  顺式-7-甲氧基cal并烯1的不对称合成是利用α-二氮杂酮7的分子内布赫纳反应作为合成途径中的关键步骤完成的。在平衡的氮杂环戊烯酮结构8还原后，所得的氮杂环戊烯9通过酸催化的芳构化过程重排为含有特征为1的6，6-元双环系统的二氢萘10。通过三步反应序列可以实现10到1的转化。
• 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.