1-Oxa<4.4.4>propella-5,7-diene | 161297-80-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: 1-Oxa<4.4.4>propella-5,7-diene
• 英文别名: 2-Oxatricyclo[4.4.4.01,6]tetradeca-7,9-diene
• CAS: 161297-80-9
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: KZWXZXRYXARECB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-甲基-1,2,4-三吖啉-3,5-二酮 、 1-Oxa<4.4.4>propella-5,7-diene 以 二氯甲烷 为溶剂， 反应 120.0h， 以70%的产率得到(4aR*,5S*,8R*,8aR*)-3,4-dihydro-N-methyl-4a,8a-butano-5,8-etheno-2H-pyrano<2,3-d>pyridazine-6,7(5H,8H)-dicarboximide
  参考文献：
  名称：

  Heteroatomic Effects on the Acid-Catalyzed Rearrangements of Dispiro[4.0.4.4]tetradeca-11,13-dienes

  摘要：

  The synthesis of dispiro [4.0.4.4]tetradeca-11,13-dienes containing one or two heteroatoms (O,S) is described. In all cases, a suitably functionalized cyclohexanone served as the precursor. Bromination-dehydrobromination delivered the cyclohexenone, which was subjected to 1,2-reduction and elimination by reaction with 2,4-dinitrobenzenesulfenyl chloride and thermal activation. The pathways by which the 1,3-cyclohexadienes undergo acid-catalyzed isomerization have been identified. The choice between aromatization and conversion to a [4.4.4]propelladiene gives evidence for being dependent on an interplay between steric and electronic factors. The generation of a transient oxonium ion causes both pathways to operate at approximately equivalent levels. When a thermodynamically less favorable thionium ion intermediate is involved, selectivity increases to the point where only aromatization occurs in the presence of p-toluenesulfonic acid. A neighboring sulfhydryl group is shown to be capable of intercepting the spirocyclic carbocationic intermediate. The regiochemistry of the epoxidation of 30 and the stereoselectivity of Diels-Alder cycloaddition of the [4.4.4]propelladienes to N-methyltriazolinedione are also detailed.

  DOI：

  10.1021/ja00096a024
• 作为产物：
  描述：

  1-oxadispiro<4.0.4.4>tetradec-12-en-14-ol 在 2,4-二硝基苯硫氯 、 对甲苯磺酸 、 三乙胺 作用下， 以 氘代氯仿 、 1,2-二氯乙烷 为溶剂， 反应 8.08h， 生成 1-Oxa<4.4.4>propella-5,7-diene
  参考文献：
  名称：

  Heteroatomic Effects on the Acid-Catalyzed Rearrangements of Dispiro[4.0.4.4]tetradeca-11,13-dienes

  摘要：

  The synthesis of dispiro [4.0.4.4]tetradeca-11,13-dienes containing one or two heteroatoms (O,S) is described. In all cases, a suitably functionalized cyclohexanone served as the precursor. Bromination-dehydrobromination delivered the cyclohexenone, which was subjected to 1,2-reduction and elimination by reaction with 2,4-dinitrobenzenesulfenyl chloride and thermal activation. The pathways by which the 1,3-cyclohexadienes undergo acid-catalyzed isomerization have been identified. The choice between aromatization and conversion to a [4.4.4]propelladiene gives evidence for being dependent on an interplay between steric and electronic factors. The generation of a transient oxonium ion causes both pathways to operate at approximately equivalent levels. When a thermodynamically less favorable thionium ion intermediate is involved, selectivity increases to the point where only aromatization occurs in the presence of p-toluenesulfonic acid. A neighboring sulfhydryl group is shown to be capable of intercepting the spirocyclic carbocationic intermediate. The regiochemistry of the epoxidation of 30 and the stereoselectivity of Diels-Alder cycloaddition of the [4.4.4]propelladienes to N-methyltriazolinedione are also detailed.

  DOI：

  10.1021/ja00096a024

文献信息

• Paquette, Leo; Branan, Bruce M., Heterocycles, 1995, vol. 40, # 1, p. 101 - 104
  作者：Paquette, Leo、Branan, Bruce M.

  DOI：——

  日期：——
• High-Pressure Diels-Alder Reactions of 1-Oxa[4.4.4]propella-5,7-diene Proceed with Framework Isomerization
  作者：Leo A. Paquette、Bruce M. Branan、Robin D. Rogers

  DOI：10.1021/jo00111a051

  日期：1995.3

  The title compound is shown to be unreactive to Diels-Alder cycloaddition under high pressure conditions. However, by virtue of acid catalysis (spontaneous or purposeful), the propelladiene experiences rearrangement to a diene isomer which, although thermodynamically less favored, is reactive toward several classical dienophiles. Extensive use has been made of 2-D NMR and X-ray crystallography in product characterization. The distributions of the adduct pairs show that the oxide atom does not exert a consistent oriental dominance on pi-facial selectivity. The heats of formation of the isomeric dienes, estimated by molecular mechanics calculations, are consistent with the experimental inability to isolate and characterize the rearrangement product.
• Branan Bruce M., Paquette Leo A., J. Amer. Chem. Soc, 116 (1994) N 17, S 7568-7667
  作者：Branan Bruce M., Paquette Leo A.

  DOI：——

  日期：——
• Heteroatomic Effects on the Acid-Catalyzed Rearrangements of Dispiro[4.0.4.4]tetradeca-11,13-dienes
  作者：Bruce M. Branan、Leo A. Paquette

  DOI：10.1021/ja00096a024

  日期：1994.8

  The synthesis of dispiro [4.0.4.4]tetradeca-11,13-dienes containing one or two heteroatoms (O,S) is described. In all cases, a suitably functionalized cyclohexanone served as the precursor. Bromination-dehydrobromination delivered the cyclohexenone, which was subjected to 1,2-reduction and elimination by reaction with 2,4-dinitrobenzenesulfenyl chloride and thermal activation. The pathways by which the 1,3-cyclohexadienes undergo acid-catalyzed isomerization have been identified. The choice between aromatization and conversion to a [4.4.4]propelladiene gives evidence for being dependent on an interplay between steric and electronic factors. The generation of a transient oxonium ion causes both pathways to operate at approximately equivalent levels. When a thermodynamically less favorable thionium ion intermediate is involved, selectivity increases to the point where only aromatization occurs in the presence of p-toluenesulfonic acid. A neighboring sulfhydryl group is shown to be capable of intercepting the spirocyclic carbocationic intermediate. The regiochemistry of the epoxidation of 30 and the stereoselectivity of Diels-Alder cycloaddition of the [4.4.4]propelladienes to N-methyltriazolinedione are also detailed.