1-oxadispiro<4.0.4.4>tetradec-12-en-14-ol | 1053658-33-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 英文名称: 1-oxadispiro<4.0.4.4>tetradec-12-en-14-ol
• 英文别名: 1-Oxadispiro[4.0.4.4]tetradec-12-en-14-ol；7-oxadispiro[4.0.46.45]tetradec-12-en-11-ol
• CAS: 1053658-33-5
• 化学式: C₁₃H₂₀O₂
• 分子量: 208.301
• InChiKey: YJIXCWYIXRYXMS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  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 3-(5,6,7,8-tetrahydro-[1]naphthyl)-propan-1-ol
  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-one 在 sodium tetrahydroborate 、 cerium(III) chloride 作用下， 以 甲醇 为溶剂， 以91%的产率得到1-oxadispiro<4.0.4.4>tetradec-12-en-14-ol
  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

• 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.