methyl 2-(3-butenyl)-3-benzoylpropionate | 172980-67-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-(3-butenyl)-3-benzoylpropionate
• CAS: 172980-67-5
• 化学式: C₁₅H₁₈O₃
• 分子量: 246.306
• InChiKey: YTHDXGLASYLFAU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.01
• 重原子数：
  18.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  methyl 2-(3-butenyl)-3-benzoylpropionate 在 Rh₂(Cap)4 potassium trimethylsilonate 、 氯甲酸甲酯 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 生成 3,5-methano-8-oxatricyclo-7-oxo-4-phenyl<3.2.1.0^1,4>octane
  参考文献：
  名称：

  Ligand-Induced Selectivity in the Rhodium(II)-Catalyzed Reactions of α-Diazo Carbonyl Compounds

  摘要：

  3-Allyl-2,5-diazopentanedione and 3-butenyl-2,5-diazopentanedione were allowed to react with a trace amount of a rhodium(II) catalyst in methylene chloride at room temperature. The major products isolated correspond to the internal trapping of a carbonyl ylide as well as intramolecular cyclopropanation. Changing the catalyst from Rh-2(OAc)(4) to Rh-2(cap)(4) to Rh-2(tfa)(4) caused a significant alteration in product distribution. A rather unusual and unexpected regiochemical crossover in the cycloaddition occurred when Rh-2(tfa)(4) was used and is most likely due to complexation of the metal with the dipole. A computational approach to rationalize the observed product distribution was carried out. The thermodynamic stabilities of cycloaddition transition states were approximated from the computationally derived strain energies of ground state molecules using traditional force-field techniques. Globally minimized ground state energies were obtained for all possible cycloaddition products, and final strain energies were calculated. In all cases studied, the lower energy isomer corresponded to the cycloadduct actually isolated. A study of the regiochemical aspects of the Rh(II)-catalyzed reaction of 1-diazo-3-(2-oxo-2-phenylethyl)hexane-2, was also carried out. Cyclization of the initially formed rhodium carbenoid occurred exclusively across the acetyl rather than the benzoyl group. The structure of the internal cycloadduct was assigned on the basis of a proton-detected multiple-bond heteronuclear multiple-quantum coherence experiment.

  DOI：

  10.1021/jo951576n
• 作为产物：
  描述：

  methyl 2-(3-butenyl)-3-benzoylpropionate ethylene ketal 在 4-甲基苯磺酸吡啶 作用下， 以 乙醚 、 丙酮 为溶剂， 反应 12.0h， 以89%的产率得到methyl 2-(3-butenyl)-3-benzoylpropionate
  参考文献：
  名称：

  Ligand-Induced Selectivity in the Rhodium(II)-Catalyzed Reactions of α-Diazo Carbonyl Compounds

  摘要：

  3-Allyl-2,5-diazopentanedione and 3-butenyl-2,5-diazopentanedione were allowed to react with a trace amount of a rhodium(II) catalyst in methylene chloride at room temperature. The major products isolated correspond to the internal trapping of a carbonyl ylide as well as intramolecular cyclopropanation. Changing the catalyst from Rh-2(OAc)(4) to Rh-2(cap)(4) to Rh-2(tfa)(4) caused a significant alteration in product distribution. A rather unusual and unexpected regiochemical crossover in the cycloaddition occurred when Rh-2(tfa)(4) was used and is most likely due to complexation of the metal with the dipole. A computational approach to rationalize the observed product distribution was carried out. The thermodynamic stabilities of cycloaddition transition states were approximated from the computationally derived strain energies of ground state molecules using traditional force-field techniques. Globally minimized ground state energies were obtained for all possible cycloaddition products, and final strain energies were calculated. In all cases studied, the lower energy isomer corresponded to the cycloadduct actually isolated. A study of the regiochemical aspects of the Rh(II)-catalyzed reaction of 1-diazo-3-(2-oxo-2-phenylethyl)hexane-2, was also carried out. Cyclization of the initially formed rhodium carbenoid occurred exclusively across the acetyl rather than the benzoyl group. The structure of the internal cycloadduct was assigned on the basis of a proton-detected multiple-bond heteronuclear multiple-quantum coherence experiment.

  DOI：

  10.1021/jo951576n