4-vinyl-3-cyclohexenol | 216392-11-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-vinyl-3-cyclohexenol
• 英文别名: 4-vinylcyclohex-3-enol；4-Ethenylcyclohex-3-en-1-ol
• CAS: 216392-11-9
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: WHHGRUKEWATTMY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  氯甲基甲基醚 、 4-vinyl-3-cyclohexenol 在 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 以95%的产率得到4-[(methoxymethyl)oxy]-1-vinylcyclohexene
  参考文献：
  名称：

  Enantioselective Diels−Alder Cycloadditions with (SS)-2-(p-Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes

  摘要：

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.

  DOI：

  10.1021/jo9811874
• 作为产物：
  描述：

  4-羟基环己酮乙二醇缩醛 在 四(三苯基膦)钯 咪唑 、 cerium(III) chloride 、 氢氟酸 、 双(三甲基硅烷基)氨基钾 、 sodium iodide 、 lithium chloride 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 19.33h， 生成 4-vinyl-3-cyclohexenol
  参考文献：
  名称：

  Enantioselective Diels−Alder Cycloadditions with (SS)-2-(p-Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes

  摘要：

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.

  DOI：

  10.1021/jo9811874

文献信息

• Acceleration Effect of an Allylic Hydroxy Group on Ring-Closing Enyne Metathesis of Terminal Alkynes: Scope, Application, and Mechanistic Insights
  作者：Tatsushi Imahori、Hidetomo Ojima、Yuichi Yoshimura、Hiroki Takahata

  DOI：10.1002/chem.200801439

  日期：——

  acceleration effect of an allylic hydroxy group on ring-closing enyne metathesis has been found. Ring-closing enyne metathesis of terminal alkynes possessing an allylic hydroxy group proceeded smoothly without the ethylene atmosphere generally necessary to promote the reaction. The synthesis of (+)-isofagomine with the aid of this efficient reaction has been demonstrated. Mechanistic studies of the acceleration

  已经发现烯丙基羟基对闭环烯炔复分解的有趣的加速作用。具有烯丙基羟基的末端炔烃的闭环烯炔复分解反应顺利进行，而通常没有促进反应所需的乙烯气氛。已经证明了借助该有效反应的（+）-异黄花碱的合成。还进行了加速作用的机理研究。NMR研究的结果表明反应是通过“烯-然后-炔”途径进行的。动力学研究表明，由于存在烯丙基羟基，导致速率确定步骤的切换。这些结果表明，烯丙基羟基加速了Ru-卡宾物质的再进入步骤。
• Enantioselective Diels−Alder Cycloadditions with (S<i>S</i>)-2-(<i>p-</i>Tolylsulfinyl)-1,4-naphthoquinone:  Efficient Kinetic Resolution of Chiral Racemic Vinylcyclohexenes
  作者：M. Carmen Carreño、Antonio Urbano、Claudio Di Vitta

  DOI：10.1021/jo9811874

  日期：1998.11.1

  Chiral racemic vinylcyclohexenes 1a-m, bearing allylic and nonallylic oxygenated substituents on the cyclohexene ring, were submitted to Diels-Alder reactions with enantiomerically pure (SS)(2-p-tolylsulfinyl)-1,4-naphthoquinone. The tandem cycloaddition/pyrolytic sulfoxide elimination led to the formation of enantiomerically enriched angularly tetracyclic quinones (+)-8a and (+)-12, arising from the kinetic resolution of the racemic diene. Dienes la-c, bearing an alkoxy substituent at the allylic position C-3, and 1d-g, with C-3 alkoxy and C-5 methyl groups, gave exclusively quinones (+)-8a-g, resulting from the anti approach to the dienophile. A similar anti selectivity occurred in cycloadditions of dienes 1ij, viith the alkoxy group situated at the allylic position C-6. Nonallylic 4-substituted vinylcyclohexenes 1k-m evolved to ca. 75:25 mixtures of (+)-anti-8k-m and (+)-syn-12k-m derivatives. In all cases, (SS)-(2-p-tolylsulfinyl)-1,4-naphthoquinone reacted from the less hindered face of the more reactive s-cis conformation, giving rise to products in moderate to excellent enantiomeric excesses. Steric effects and torsional interactions in the corresponding approaches account for the observed pi-facial diastereoselectivities at both partners.