1-hydroxy-5-phenyl-4-(2-propenyl)-2,5-pentanedione

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-hydroxy-5-phenyl-4-(2-propenyl)-2,5-pentanedione
• 英文别名: 2-allyl-5-hydroxy-1-phenylpentane-1,4-dione；5-Hydroxy-1-phenyl-2-prop-2-enylpentane-1,4-dione
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: IONGCBLJYKQZNG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-hydroxy-5-phenyl-4-(2-propenyl)-2,5-pentanedione 在 sodium hydroxide 作用下， 以 乙醚 、 水 为溶剂， 反应 3.0h， 以75 mg的产率得到4-allyl-2-hydroxy-3-phenylcyclopent-2-en-1-one
  参考文献：
  名称：

  从酰基氰醇方便且容易地获得2-羟基环戊-2-烯酮

  摘要：

  通过在基本条件下使用钛环丙烷配合物作为亲核配偶体和分子内羟醛缩合，从酰基氰醇设计了一种方便的2-羟基环戊烯酮。一锅法的发展允许一步和原子经济的过程，并且使用除乙基溴化镁以外的格氏试剂可提供有价值的3,4-二取代的2-羟基环戊烯酮。通过使用钯介导的交叉偶联反应进一步α-位官能化，说明了羟基的用途。

  DOI：

  10.1016/j.tet.2019.07.010
• 作为产物：
  描述：

  3-苯基丙酸甲酯 在 tetrakis(trifluoroacetato)rhodium(II) potassium trimethylsilonate 、 4-甲基苯磺酸吡啶 、 对甲苯磺酸 、 氯甲酸甲酯 、 lithium diisopropyl amide 作用下， 以 乙醚 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 反应 59.0h， 生成 1-hydroxy-5-phenyl-4-(2-propenyl)-2,5-pentanedione
  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

文献信息

• Ligand-Induced Selectivity in the Rhodium(II)-Catalyzed Reactions of α-Diazo Carbonyl Compounds
  作者：Albert Padwa、David J. Austin、Susan F. Hornbuckle

  DOI：10.1021/jo951576n

  日期：1996.1.1

  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.
• Convenient and easy access to 2-hydroxycyclopent-2-enones from acylcyanohydrins
  作者：Mathilde Pantin、Florent Bodinier、Jordan Saillour、Yassine M. Youssouf、Fabien Boeda、Morwenna S.M. Pearson-Long、Philippe Bertus

  DOI：10.1016/j.tet.2019.07.010

  日期：2019.8

  A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones

  通过在基本条件下使用钛环丙烷配合物作为亲核配偶体和分子内羟醛缩合，从酰基氰醇设计了一种方便的2-羟基环戊烯酮。一锅法的发展允许一步和原子经济的过程，并且使用除乙基溴化镁以外的格氏试剂可提供有价值的3,4-二取代的2-羟基环戊烯酮。通过使用钯介导的交叉偶联反应进一步α-位官能化，说明了羟基的用途。