1,5-diisopropyl-2,4-dimethyl-1,4-pentadien-3-one | 217076-65-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,5-diisopropyl-2,4-dimethyl-1,4-pentadien-3-one
• 英文别名: (3E,6E)-2,4,6,8-tetramethylnona-3,6-dien-5-one
• CAS: 217076-65-8
• 化学式: C₁₃H₂₂O
• 分子量: 194.317
• InChiKey: DIOKEQQBTUCKPN-MKICQXMISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  1,5-diisopropyl-2,4-dimethyl-1,4-pentadien-3-one 在 三乙基硅烷 、 三氟化硼乙醚 、 盐酸 作用下， 以 二氯甲烷 为溶剂， 以84%的产率得到(3S,4S)-3,4-Diisopropyl-2,5-dimethyl-cyclopentanone
  参考文献：
  名称：

  Ionic Hydrogenation of Oxyallyl Intermediates: The Reductive Nazarov Cyclization

  摘要：

  Cyclization of tri- and tetrasubstituted dienones 1 under Lewis acidic conditions in the presence of triethylsilane led to formation of either silyl enol ethers 6 or cyclopentanones 7 in good to excellent yields, depending on work-up conditions. The proposed mechanism involves initial Nazarov cyclization to give oxyallyl intermediates 5, which are intercepted via intermolecular transfer of hydride. The reactions proceeded cleanly with as little as 2 equiv. of silane and in most cases catalytic amounts of Lewis acid could be used. Trapping with Et3SiD occurs at the less substituted terminus in unsymmetrical cases. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00866-8
• 作为产物：
  描述：

  异丁醛 、 3-戊酮 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 以8%的产率得到1,5-diisopropyl-2,4-dimethyl-1,4-pentadien-3-one
  参考文献：
  名称：

  Ionic Hydrogenation of Oxyallyl Intermediates: The Reductive Nazarov Cyclization

  摘要：

  Cyclization of tri- and tetrasubstituted dienones 1 under Lewis acidic conditions in the presence of triethylsilane led to formation of either silyl enol ethers 6 or cyclopentanones 7 in good to excellent yields, depending on work-up conditions. The proposed mechanism involves initial Nazarov cyclization to give oxyallyl intermediates 5, which are intercepted via intermolecular transfer of hydride. The reactions proceeded cleanly with as little as 2 equiv. of silane and in most cases catalytic amounts of Lewis acid could be used. Trapping with Et3SiD occurs at the less substituted terminus in unsymmetrical cases. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00866-8

文献信息

• Construction of aryl-substituted triquinanes through the interrupted Nazarov reaction
  作者：Curtis J. Rieder、Ryan J. Fradette、F. G. West

  DOI：10.1039/b800800k

  日期：——

  The first examples of intermolecular trapping of Nazarov cyclopentenyl cation intermediates by simple arenes to furnish alpha-arylcyclopentanones are described.

  描述了通过简单的芳烃分子间捕获Nazarov环戊烯基阳离子中间体以提供α-芳基环戊烯酮的第一个实例。
• Polymer-Mediated Reactions. A Nazarov-Like Cyclization
  作者：Michael Smith、Christopher Pavlik、Martha Morton、Michael Invernale、Ian Berghorn、Gregory Sotzing

  DOI：10.1055/s-0030-1261194

  日期：2011.9

  The polymer PEDOT+ mediates a Nazarov-like cyclization of dienones, in an heterogeneous system and in hydrocarbon solvents. The polymer-mediated reactions show clear differences in product formation when compared to the same reaction with tosic acid, or when compared to reports in the literature. Comparable or improved yields are observed, as well as the ability to give a Nazarov product in cases where treatment with acid fails to give cyclization, or leads to an undesirable rearrangement. In addition, the ability to recycle the polymer makes this a potentially useful protocol for an important organic chemical reaction.
• The reductive Nazarov cyclization
  作者：Sören Giese、F.G. West

  DOI：10.1016/s0040-4039(98)01934-0

  日期：1998.11

  Tri- and tetrasubstituted 1,4-dien-3-ones 1 were treated with Lewis acid in the presence of triethylsilane, furnishing either silyl enol ethers 4 or cyclopentanones 5 in good yields, depending upon work-up conditions. This reaction is presumed to occur through oxyallyl intermediate 3, which undergoes intermolecular hydride transfer and O-silylation to give 4. In most cases, only 2 equiv. of silane was required, and catalytic amounts of Lewis acid could be used. Trienone substrate 7 was found to undergo clean conversion to tricyclic ether 8, indicating fast capture of the oxyallyl intermediate by the pendant olefin. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Efficient intermolecular 3+2 trapping of the Nazarov intermediate with vinyl sulfides
  作者：Bahja Mahmoud、F.G. West

  DOI：10.1016/j.tetlet.2007.05.093

  日期：2007.7

  Cross-conjugated 1,4-pentadien-3-ones undergo electrocyclization to 2-oxidocyclopentenyl cations upon treatment with BF3-OEt2, When these reactions are carried out in the presence of electron-rich vinyl sulfides, nucleophilic trapping followed by ring-closure furnishes bridged bicyclic products that can be viewed as formal 3+2 cycloadducts. This process results in three new carbon-carbon bonds and establishes up to five new stereocenters. (C) 2007 Elsevier Ltd. All rights reserved.
• Ionic Hydrogenation of Oxyallyl Intermediates: The Reductive Nazarov Cyclization
  作者：Sören Giese、F.G. West

  DOI：10.1016/s0040-4020(00)00866-8

  日期：2000.12

  Cyclization of tri- and tetrasubstituted dienones 1 under Lewis acidic conditions in the presence of triethylsilane led to formation of either silyl enol ethers 6 or cyclopentanones 7 in good to excellent yields, depending on work-up conditions. The proposed mechanism involves initial Nazarov cyclization to give oxyallyl intermediates 5, which are intercepted via intermolecular transfer of hydride. The reactions proceeded cleanly with as little as 2 equiv. of silane and in most cases catalytic amounts of Lewis acid could be used. Trapping with Et3SiD occurs at the less substituted terminus in unsymmetrical cases. (C) 2000 Elsevier Science Ltd. All rights reserved.