syn-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: syn-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-en-2-one
• 英文别名: (1S,5S,6S)-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-en-2-one
• 化学式: C₆H₆O₃
• 分子量: 126.112
• InChiKey: HHEPZGQHWOPVMS-ZXEDONINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.7
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  syn-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-en-2-one 在 咪唑 、 三丁基膦 、 三乙基铝 、 氟化氢吡啶 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 dl-isoepoxydon
  参考文献：
  名称：

  The synthesis of epi-epoxydon utilising the Baylis–Hillman reaction

  摘要：

  -(+/-)-epi-Epoxydon was synthesised by means of a triethylaluminium/ tri-n-butylphosphine-catalysed Baylis-Hillman reaction between an O-protected epoxidised hydroxyquinol core and paraformaldehyde, constituting the first application of the Baylis-Hillman reaction to a highly functionalised beta-substituted enone. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)00529-4
• 作为产物：
  描述：

  1,4-环己二烯 在 titanium(IV) isopropylate 、 5,10,15,20-tetrakisphenylporphyrin 、 cobalt(II) 5,10,15,20-tetraphenylporphyrin 、 乙硫醚 、 氧气 、 silica gel 、 pyridinium chlorochromate 作用下， 以 正己烷 、 二氯甲烷 、 氯仿 、 乙酸乙酯 为溶剂， 反应 30.08h， 生成 syn-5-hydroxy-7-oxabicyclo[4.1.0]hept-3-en-2-one
  参考文献：
  名称：

  2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one:  Synthesis and Reactions of the Keto Endoperoxide of Phenol

  摘要：

  The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.

  DOI：

  10.1021/jo000120p

文献信息

• 2,3-Dioxabicyclo[2.2.2]oct-7-en-5-one:  Synthesis and Reactions of the Keto Endoperoxide of Phenol
  作者：Waldemar Adam、Metin Balci、Hamdullah Kiliç

  DOI：10.1021/jo000120p

  日期：2000.9.1

  The photooxygenation of 1,4-cyclohexadiene (3) affords the diastereomeric hydroperoxy endoperoxides exo-4 and endo-4 and the diastereomeric hydroperoxides trans-5 and cis-5 in a ratio of 87: 9:3.5:0.5. Selective reduction of hydroperoxide group in the endoperoxides exo-4 and endo-4 in the presence of titanium tetraisopropoxide-diethyl sulfide gave the corresponding hydroxy endoperoxides exo-7 and endo-7, which on PCC oxidation leads to the phenol-derived keto endoperoxide 2. The triphenylphosphine deoxygenation of the keto endoperoxide 2 produces a 9:1 mixture of 1,2- and 1,4-dihydroxybenzenes 10 and 11, while the CoTPP-catalyzed rearrangement affords the bisepoxide 12, malealdehyde (13), and beta-lactone 14. The mechanisms of these transformations are presented.
• The synthesis of epi-epoxydon utilising the Baylis–Hillman reaction
  作者：Thorsten Genski、Richard J.K. Taylor

  DOI：10.1016/s0040-4039(02)00529-4

  日期：2002.5

  -(+/-)-epi-Epoxydon was synthesised by means of a triethylaluminium/ tri-n-butylphosphine-catalysed Baylis-Hillman reaction between an O-protected epoxidised hydroxyquinol core and paraformaldehyde, constituting the first application of the Baylis-Hillman reaction to a highly functionalised beta-substituted enone. (C) 2002 Elsevier Science Ltd. All rights reserved.