2-<1-carbomethoxyhepta-4(E),6-dienyl>-2,4,6-cycloheptatrien-1-one | 115912-67-9

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物 - 环庚三烯酮
• 英文名称: 2-<1-carbomethoxyhepta-4(E),6-dienyl>-2,4,6-cycloheptatrien-1-one
• 英文别名: 2-(1-carbomethoxy-4,6-heptadien-1-yl)-2,4,6-cycloheptatrien-1-one；methyl (5E)-2-(7-oxocyclohepta-1,3,5-trien-1-yl)octa-5,7-dienoate
• CAS: 115912-67-9
• 化学式: C₁₆H₁₈O₃
• 分子量: 258.317
• InChiKey: RKIXMQMMURUAFC-SNAWJCMRSA-N

物化性质

• 沸点：
  411.3±44.0 °C(predicted)
• 密度：
  1.067±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-<1-carbomethoxyhepta-4(E),6-dienyl>-2,4,6-cycloheptatrien-1-one 以 苯 为溶剂， 反应 24.0h， 以87%的产率得到1,2,3,8,9,11a-hexahydro-3a,8-methano-3-carbomethoxy-3aH-cyclopenta-cyclodecen-12-one
  参考文献：
  名称：

  Studies on Intramolecular Higher-Order Cycloaddition Reactions

  摘要：

  Thermal, metal-free, and metal-promoted intramolecular higher-order cycloadditions are described. Substrates in which the tropone (2,4,6-cycloheptatrien-1-one) nucleus is tethered to various diene moieties undergo exo-selective [6 pi + 4 pi] cycloaddition under thermal conditions to afford stereochemically defined tricyclic products. The substrates employed in this study were prepared by addition of the Grignard derivative of the given diene side-chain unit to 2-chlorotropone, In each instance, the requisite 2-substituted tropone was obtained directly from these reaction sequences. A similar study was conducted on the corresponding chromium(0) complexes of related tropone and cycloheptatriene-based substrates. In the cases involving metal mediation both thermal and photochemical activation were effective for delivering cycloadducts. The metal-promoted reactions were shown to proceed exclusively via an endo-selective pathway, which is stereocomplementary to the course of the thermal, metal-free reactions. A tandem Cr(0)-promoted 1,5-H shift-[6 pi+2 pi] cycloaddition protocol is also reported with several systems.

  DOI：

  10.1021/jo9518009
• 作为产物：
  描述：

  methyl (5E)-5,7-octadienoate 、 2-氯-2,4,6-环庚三烯-1-酮 在 正丁基锂 、 二异丙胺 作用下， 生成 2-<1-carbomethoxyhepta-4(E),6-dienyl>-2,4,6-cycloheptatrien-1-one
  参考文献：
  名称：

  Studies on Intramolecular Higher-Order Cycloaddition Reactions

  摘要：

  Thermal, metal-free, and metal-promoted intramolecular higher-order cycloadditions are described. Substrates in which the tropone (2,4,6-cycloheptatrien-1-one) nucleus is tethered to various diene moieties undergo exo-selective [6 pi + 4 pi] cycloaddition under thermal conditions to afford stereochemically defined tricyclic products. The substrates employed in this study were prepared by addition of the Grignard derivative of the given diene side-chain unit to 2-chlorotropone, In each instance, the requisite 2-substituted tropone was obtained directly from these reaction sequences. A similar study was conducted on the corresponding chromium(0) complexes of related tropone and cycloheptatriene-based substrates. In the cases involving metal mediation both thermal and photochemical activation were effective for delivering cycloadducts. The metal-promoted reactions were shown to proceed exclusively via an endo-selective pathway, which is stereocomplementary to the course of the thermal, metal-free reactions. A tandem Cr(0)-promoted 1,5-H shift-[6 pi+2 pi] cycloaddition protocol is also reported with several systems.

  DOI：

  10.1021/jo9518009

文献信息

• Lithium enolate additions to the tropone nucleus
  作者：James H. Rigby、Chrisantha H. Senanayake、Sushil Rege

  DOI：10.1021/jo00254a040

  日期：1988.9
• RIGBY, JAMES H.;SENANAYAKE, CHRISANTHA H.;REGE, SUSHIL, J. ORG. CHEM., 53,(1988) N 19, C. 4596-4598
  作者：RIGBY, JAMES H.、SENANAYAKE, CHRISANTHA H.、REGE, SUSHIL

  DOI：——

  日期：——