4-allyl-2-(1-hexynyl)-3-isopropoxy-4-(4-methoxyphenyl)-2-cyclobutenone | 231611-45-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 4-allyl-2-(1-hexynyl)-3-isopropoxy-4-(4-methoxyphenyl)-2-cyclobutenone
• 英文别名: 2-Hex-1-ynyl-4-(4-methoxyphenyl)-3-propan-2-yloxy-4-prop-2-enylcyclobut-2-en-1-one
• CAS: 231611-45-3
• 化学式: C₂₃H₂₈O₃
• 分子量: 352.474
• InChiKey: DWRWQLBEEQHNRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-allyl-2-(1-hexynyl)-3-isopropoxy-4-(4-methoxyphenyl)-2-cyclobutenone 在 三氟化硼乙醚 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 5.5h， 生成 2-(1-hexynyl)-3-isopropoxy-7-methoxy-4-(2-methylallyl)naphthol
  参考文献：
  名称：

  Synthesis and Thermal Rearrangements of 4-Allyl-4-arylcyclobutenones

  摘要：

  The synthesis and thermolysis of 4-allyl-4-arylcyclobutenones are detailed. Allylcyclobutenones were prepared through the trapping of the cyclobutenonium cation generated by treatment of 4-hydroxycyclobutenones with Lewis acids. A study of the nucleophilic trapping revealed the following mechanistic highlights: the most likely intermediate is the cyclobutenonium cation, the regioselectivity of the allylation reaction is dictated by attack at the site most suited to stabilize the cation, and the rate of allylation is dependent on carbocation formation. Thermolysis of 4-allyl-4-arylcyclobutenones made possible a study of the competitive [2 + 2] cycloaddition and 6 pi electrocyclization. A judicious choice of substituents allows some control of the selectivity between the two pathways. The substituents control this selectivity through a combination of imposed electronics in the dienylketene intermediate, the relative ketenophilicity of the 4-position substituent, and the relative contortion substituents in the 2- and S-positions impose on the transition state of the respective ring-closure processes. The scope of the cyclobutenonium cation trapping with silylated carbon nucleophiles was explored, producing 4-allenylcyclobutenones from the use of propargylsilane and 4-spirocyclobutenones from triisopropylsilane. Thermolysis studies of these precursors are also detailed.

  DOI：

  10.1021/jo990052a
• 作为产物：
  描述：

  2-(1-hexynyl)-4-hydroxy-3-isopropoxy-4-(4-methoxyphenyl)-2-cyclobutenone 、 烯丙基三甲基硅烷 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 以96%的产率得到4-allyl-2-(1-hexynyl)-3-isopropoxy-4-(4-methoxyphenyl)-2-cyclobutenone
  参考文献：
  名称：

  Synthesis and Thermal Rearrangements of 4-Allyl-4-arylcyclobutenones

  摘要：

  The synthesis and thermolysis of 4-allyl-4-arylcyclobutenones are detailed. Allylcyclobutenones were prepared through the trapping of the cyclobutenonium cation generated by treatment of 4-hydroxycyclobutenones with Lewis acids. A study of the nucleophilic trapping revealed the following mechanistic highlights: the most likely intermediate is the cyclobutenonium cation, the regioselectivity of the allylation reaction is dictated by attack at the site most suited to stabilize the cation, and the rate of allylation is dependent on carbocation formation. Thermolysis of 4-allyl-4-arylcyclobutenones made possible a study of the competitive [2 + 2] cycloaddition and 6 pi electrocyclization. A judicious choice of substituents allows some control of the selectivity between the two pathways. The substituents control this selectivity through a combination of imposed electronics in the dienylketene intermediate, the relative ketenophilicity of the 4-position substituent, and the relative contortion substituents in the 2- and S-positions impose on the transition state of the respective ring-closure processes. The scope of the cyclobutenonium cation trapping with silylated carbon nucleophiles was explored, producing 4-allenylcyclobutenones from the use of propargylsilane and 4-spirocyclobutenones from triisopropylsilane. Thermolysis studies of these precursors are also detailed.

  DOI：

  10.1021/jo990052a

文献信息

• Synthesis and Thermal Rearrangements of 4-Allyl-4-arylcyclobutenones
  作者：Ralf Tiedemann、Philip Turnbull、Harold W. Moore

  DOI：10.1021/jo990052a

  日期：1999.5.1

  The synthesis and thermolysis of 4-allyl-4-arylcyclobutenones are detailed. Allylcyclobutenones were prepared through the trapping of the cyclobutenonium cation generated by treatment of 4-hydroxycyclobutenones with Lewis acids. A study of the nucleophilic trapping revealed the following mechanistic highlights: the most likely intermediate is the cyclobutenonium cation, the regioselectivity of the allylation reaction is dictated by attack at the site most suited to stabilize the cation, and the rate of allylation is dependent on carbocation formation. Thermolysis of 4-allyl-4-arylcyclobutenones made possible a study of the competitive [2 + 2] cycloaddition and 6 pi electrocyclization. A judicious choice of substituents allows some control of the selectivity between the two pathways. The substituents control this selectivity through a combination of imposed electronics in the dienylketene intermediate, the relative ketenophilicity of the 4-position substituent, and the relative contortion substituents in the 2- and S-positions impose on the transition state of the respective ring-closure processes. The scope of the cyclobutenonium cation trapping with silylated carbon nucleophiles was explored, producing 4-allenylcyclobutenones from the use of propargylsilane and 4-spirocyclobutenones from triisopropylsilane. Thermolysis studies of these precursors are also detailed.