1β,5-Epoxy-(4αH,7αH,10αH)-guajen-(12) | 10224-59-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1β,5-Epoxy-(4αH,7αH,10αH)-guajen-(12)
• 英文别名: (1S,2S,5R,7S,8S)-2,8-dimethyl-5-prop-1-en-2-yl-11-oxatricyclo[5.3.1.01,7]undecane
• CAS: 10224-59-6
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: RGRYQUWGSJPMMK-RMEBNNNOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (-)-愈创醇 在 4-二甲氨基吡啶 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.5h， 生成 1α,5-Epoxy-(4αH,7αH,10αH)-guajen-(12) 、 1β,5-Epoxy-(4αH,7αH,10αH)-guajen-(12)
  参考文献：
  名称：

  Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-epi-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol

  摘要：

  The diastereomeric ratio of epoxidation of the internally bridged carbon-carbon double bond of guaiol (1a) is strongly influenced by the combined effects of the types of remote protecting groups on the hydroxyisopropyl side chain, choice of solvent, and epoxidizing reagent. This observation has allowed us to devise concise stereoselective syntheses of a range of guaiane-type sesquiterpenoids via an epoxidation, ring-opening/elimination, and functionality manipulation sequence. Natural products guaia-4(5)-en-11-ol (2a), guaia-5(6)-en-11-ol (3), and aciphyllene (4a) and epimers of the recently isolated natural products, 1-epi-guaia-4(5)-en-11-ol (2b), 1-epi-aciphyllene (4b), and 1-epi-melicodenones C (5a) and E (6a), were synthesized in good yields in relatively few steps.

  DOI：

  10.1021/np500611z

文献信息

• Mechanistic Studies on the Autoxidation of α-Guaiene: Structural Diversity of the Sesquiterpenoid Downstream Products
  作者：An-Cheng Huang、Mark A. Sefton、Christopher J. Sumby、Edward R. T. Tiekink、Dennis K. Taylor

  DOI：10.1021/np500819f

  日期：2015.1.23

  and 5a/b) were also formed in significant amounts after autoxidation. Their structures were elucidated on the basis of spectroscopic data and X-ray crystallography, and a number of them were confirmed through total synthesis. The mechanisms of formation of the majority of the products may be accounted for by initial formation of the 2- and 4-hydroperoxyguaienes (6a/b and 10a/b) followed by various fragmentation

  在纤维素滤纸上，从双环倍半萜烯α-番石榴烯（1）的自氧化混合物中分离出了两种不稳定的氢过氧化物6b和10a，以及13种下游的倍半萜类化合物。分离出的重要天然产物之一是鱼藤酮（2），它是唯一已知的具有胡椒香气的冲击性气味剂。其它产物包括corymbolone（图4a）和它的C-6差向异构体4b中，第（2 - [R ）-和（2小号）-rotundols（7A / b）和天然chabrolidione A，即，7-表的几个迄今未知的差向异构体-查波利二酮A（3a）和1,7-外延- chabrolidione A（图3b）。自氧化后，还大量形成了两个4-羟基罗丹酮（8a / b）和一系列环氧化物（9a / b和5a / b）。根据光谱数据和X射线晶体学阐明了它们的结构，并通过全合成证实了其中许多。大部分产物的形成机理可能是由2-和4-氢过氧化愈创木酚（6a / b和10a / b），然后是各种破碎
• Synthesis of Guaia-4(5)-en-11-ol, Guaia-5(6)-en-11-ol, Aciphyllene, 1-<i>epi</i>-Melicodenones C and E, and Other Guaiane-Type Sesquiterpenoids via the Diastereoselective Epoxidation of Guaiol
  作者：An-Cheng Huang、Christopher J. Sumby、Edward R. T. Tiekink、Dennis K. Taylor

  DOI：10.1021/np500611z

  日期：2014.11.26

  The diastereomeric ratio of epoxidation of the internally bridged carbon-carbon double bond of guaiol (1a) is strongly influenced by the combined effects of the types of remote protecting groups on the hydroxyisopropyl side chain, choice of solvent, and epoxidizing reagent. This observation has allowed us to devise concise stereoselective syntheses of a range of guaiane-type sesquiterpenoids via an epoxidation, ring-opening/elimination, and functionality manipulation sequence. Natural products guaia-4(5)-en-11-ol (2a), guaia-5(6)-en-11-ol (3), and aciphyllene (4a) and epimers of the recently isolated natural products, 1-epi-guaia-4(5)-en-11-ol (2b), 1-epi-aciphyllene (4b), and 1-epi-melicodenones C (5a) and E (6a), were synthesized in good yields in relatively few steps.