(E)-7-hydroxy-1-phenylhept-5-en-1-one | 217454-50-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-7-hydroxy-1-phenylhept-5-en-1-one
• 英文别名: (E)-7-hydroxy-5-heptenophenone
• CAS: 217454-50-7
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: JZZMSZRGIRIFBY-FARCUNLSSA-N

物化性质

• 沸点：
  355.0±35.0 °C(predicted)
• 密度：
  1.049±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-7-hydroxy-1-phenylhept-5-en-1-one 在 indium 、 溴 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 24.5h， 生成
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s
• 作为产物：
  描述：

  (4-cyanobutyl)triphenylphosphonium bromide 在 盐酸 、 偶氮二异丁腈 、 双(三甲基硅烷基)氨基钾 、 苯硫酚 作用下， 以 苯 为溶剂， 反应 11.75h， 生成 (E)-7-hydroxy-1-phenylhept-5-en-1-one
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s

文献信息

• Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups
  作者：Youwei Xie、Paul E. Floreancig

  DOI：10.1002/anie.201402010

  日期：2014.5.5

  Allylic alcohols undergo transposition reactions in the presence of Re2O7 whereby the equilibrium can be dictated by trapping one isomer with a pendent electrophile. Additional ionization can occur when the trapping group is an aldehyde or ketone, thus leading to cyclic oxocarbenium ion formation. Terminating the process through bimolecular nucleophilic addition into the intermediate provides a versatile

  烯丙醇在Re 2 O 7的存在下进行转座反应，从而可以通过用一种亲电亲和剂捕获一种异构体来控制平衡。当捕获基团是醛或酮时，可能会发生其他电离，从而导致形成环氧碳鎓离子。通过将双分子亲核加成至中间物来终止该过程，为合成各种含氧杂环化合物提供了一种通用的方法。了解序列中各步骤的相对速率会导致设计反应，从而创建多个具有良好至极佳控制水平的立体中心。