(1S,3R,5S,8S)-3-Methoxy-3-methyl-5-phenyl-9,10-dioxa-tricyclo[6.2.1.0^1,6]undec-6-ene

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1S,3R,5S,8S)-3-Methoxy-3-methyl-5-phenyl-9,10-dioxa-tricyclo[6.2.1.0^1,6]undec-6-ene
• 英文别名: (1S,3R,5S,8S)-3-methoxy-3-methyl-5-phenyl-9,10-dioxatricyclo[6.2.1.01,6]undec-6-ene
• 化学式: C₁₇H₂₀O₃
• 分子量: 272.344
• InChiKey: QXQIYHNFFNESBA-WTTBNOFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-Methoxy-3-methyl-5-phenylbicyclo<4.3.0>nona-1(6),7-diene 在 氧气 、 焦磷酸硫胺素 作用下， 以 二氯甲烷 为溶剂， 生成 (1S,3R,5S,8S)-3-Methoxy-3-methyl-5-phenyl-9,10-dioxa-tricyclo[6.2.1.0^1,6]undec-6-ene 、 (1S,3S,5S,8S)-3-Methoxy-3-methyl-5-phenyl-9,10-dioxa-tricyclo[6.2.1.0^1,6]undec-6-ene
  参考文献：
  名称：

  Singlet Oxygen Photooxygenation of Tricyclo[4.3.0.01,3]nona-6,8-dienes and Bicyclo[4.3.0]nona-1(6),7-dienes: Characterization of the Primary Reaction Products and Subsequent Transformations

  摘要：

  Ring expansion of 3-methyl-1-phenyl-1,2-dihydropentalene 1 using a sequence of cyclopropanation and acid-catalyzed vinylcyclopropane rearrangement in the presence of nucleophilic trapping reagents led to bicyclo[4.3.0]nona-1(6),7-dienes 8 and 9 in good yields and with high diastereoselectivity. Photooxygenation of these compounds, as well as the secondary product tricyclo[4.3.0.0(1,3)]nona-6,8-diene 2, afforded the unstable endoperoxides 3 and 11 both with high (but completely inverse) diastereofacial selectivity. Both endoperoxides underwent Kornblum-De La Mare reaction in the presence of triethylamine to give the hydroxy enones 4 and 15. X-ray structure analyses of 4a and 15 confirmed the proposed reaction topicities. The thermal rearrangement of 11 afforded a series of products (bis-epoxide 12, epoxy enone 13, and epoxy enal 14) following the well-known peroxide homolysis protocol, whereas 3 thermally rearranged into the cyclooctene dione 5 and the cycloheptenone aldehyde 6, by cleavage of the central bicyclo[3.3.0]octane bond and competing 1,2-hydrogen and 1,2-alkyl shifts, respectively.

  DOI：

  10.1021/jo00112a013