2--2,4,6-cycloheptatrien-1-one | 102438-31-3

• 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--2,4,6-cycloheptatrien-1-one
• 英文别名: 2-[(4E)-hepta-4,6-dienyl]cyclohepta-2,4,6-trien-1-one
• CAS: 102438-31-3
• 化学式: C₁₄H₁₆O
• 分子量: 200.28
• InChiKey: WZLUKXKPIOUVDE-ONEGZZNKSA-N

物化性质

• 沸点：
  338.1±12.0 °C(Predicted)
• 密度：
  0.965±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2--2,4,6-cycloheptatrien-1-one 在 tris(acetonitrile)tricarbonylchromium 、 三甲氧基磷 作用下， 生成 1,2,3,8,9,11a-hexahydro-3a,8-methano-3aH-cyclopentacyclodecen-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：

  2-氯-2,4,6-环庚三烯-1-酮 、 (E)-7-bromohepta-1,3-diene 在 碘 、 magnesium 、 1,2-二溴乙烷 作用下， 生成 2--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

• Synthetic studies on the ingenane diterpenes. Inter- and intramolecular [6 + 4] tropone-diene cycloaddition reactions
  作者：James H. Rigby、Terry L. Moore、Sushil Rege

  DOI：10.1021/jo00362a051

  日期：1986.6
• Construction of the ingenane core using an Fe(III) or Ti(IV) Lewis acid-catalyzed intramolecular [6+4] cycloaddition
  作者：James H. Rigby、Mike Fleming

  DOI：10.1016/s0040-4039(02)02159-7

  日期：2002.11

  A facile entry into the ingenane core using a Lewis acid-catalyzed intramolecular [6+4] cycloaddition has been developed. Ti(IV)- and Fe(III)-based Lewis acids were found to mediate the higher order cycloaddition in good to excellent yield at room temperature. Chiral Ti(IV) Lewis acids were found to induce modest asymmetry in the resultant [6+4] cycloadducts. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Studies on Intramolecular Higher-Order Cycloaddition Reactions
  作者：James H. Rigby、Sushil D. Rege、Vincent P. Sandanayaka、Margarita Kirova

  DOI：10.1021/jo9518009

  日期：1996.1.1

  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.