(5E)-2,2,5,10-tetramethyl-3-methylideneundeca-5,9-dien-4-one | 209004-35-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (5E)-2,2,5,10-tetramethyl-3-methylideneundeca-5,9-dien-4-one
• CAS: 209004-35-3
• 化学式: C₁₆H₂₆O
• 分子量: 234.382
• InChiKey: KESPKQHFHBTUPX-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  (5E)-2,2,5,10-tetramethyl-3-methylideneundeca-5,9-dien-4-one 在 三乙基硅烷 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以81%的产率得到(2aR,4aR,6R,6aS,6bS)-6-tert-Butyl-2,2,6b-trimethyl-octahydro-pentaleno[1,6-bc]furan
  参考文献：
  名称：

  The reductive Nazarov cyclization

  摘要：

  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.

  DOI：

  10.1016/s0040-4039(98)01934-0
• 作为产物：
  描述：

  (E)-2,7-dimethyl-2,6-octadienal 在 barium permanganate 作用下， 以 二氯甲烷 为溶剂， 生成 (5E)-2,2,5,10-tetramethyl-3-methylideneundeca-5,9-dien-4-one
  参考文献：
  名称：

  无环三烯酮的高度非对映选择性环化。中断的纳扎罗夫反应。

  摘要：

  DOI：

  10.1021/jo9803030

文献信息

• 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.
• 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.
• Highly Diastereoselective Cycloisomerization of Acyclic Trienones. The Interrupted Nazarov Reaction
  作者：John A. Bender、Alan E. Blize、Cindy C. Browder、Sören Giese、F. G. West

  DOI：10.1021/jo9803030

  日期：1998.4.1