(5RS,6RS)-5-methyl-6-(prop-1-en-2-yl)spiro[1,2,4-trioxacyclohexane-3,2'-adamantane]

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 三氧烷
• 英文名称: (5RS,6RS)-5-methyl-6-(prop-1-en-2-yl)spiro[1,2,4-trioxacyclohexane-3,2'-adamantane]
• 英文别名: (5R,6R)-5-methyl-6-prop-1-en-2-ylspiro[1,2,4-trioxane-3,2'-adamantane]
• 化学式: C₁₆H₂₄O₃
• 分子量: 264.365
• InChiKey: FDVWRLAYGRZRQX-YINFPWJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  金刚烷酮 、 3-hydroperoxy-4-methyl-4-penten-2-ol 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以12%的产率得到(5RS,6RS)-5-methyl-6-(prop-1-en-2-yl)spiro[1,2,4-trioxacyclohexane-3,2'-adamantane]
  参考文献：
  名称：

  A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions

  摘要：

  II型光氧化（单重态氧）被描述为一种合成上有用的方法，用于通过感光剂吸附或共价掺杂感光剂的聚合物（宏观或纳米尺寸）容器合成烯丙基过氧化氢和端过氧化物。这些技术相比于溶液相光化学的优点在于可以促进产物的分离和纯化，并提高反应活性。通过II型光氧化生成的产物已被用于合成众多具有共同1,2,4-三氧烯核心的多环过氧化物，这在天然抗疟药青蒿素中得到了体现。

  DOI：

  10.1055/s-2005-872103

文献信息

• A Family of New 1,2,4-Trioxanes by Photooxygenation of Allylic Alcohols in Sensitizer-Doped Polymers and Secondary Reactions
  作者：Axel G. Griesbeck、Anna Bartoschek、Tamer T. El-Idreesy、Lars-Oliver Höinck、Johann Lex、Claus Miara、Jörg M. Neudörfl

  DOI：10.1055/s-2005-872103

  日期：——

  Type II photooxygenation (singlet oxygen) is described as a synthetically useful way for the preparation of allylic hydro­peroxides and endoperoxides using sensitizer-adsorbed or covalently sensitizer-doped polymeric (macro- or nanosized) containers. Facilitated product separation and purification as well as increased reactivity are advantages of these techniques in comparison with solution-phase photochemistry. The products generated by Type II photooxygenation have been used for the syntheses of numerous polycyclic peroxides with a common 1,2,4-trioxane core as exhibited in the natural antimalarial artemisinin.

  II型光氧化（单重态氧）被描述为一种合成上有用的方法，用于通过感光剂吸附或共价掺杂感光剂的聚合物（宏观或纳米尺寸）容器合成烯丙基过氧化氢和端过氧化物。这些技术相比于溶液相光化学的优点在于可以促进产物的分离和纯化，并提高反应活性。通过II型光氧化生成的产物已被用于合成众多具有共同1,2,4-三氧烯核心的多环过氧化物，这在天然抗疟药青蒿素中得到了体现。
• Novel spiroanellated 1,2,4-trioxanes with high in vitro antimalarial activities
  作者：Axel G. Griesbeck、Tamer T. El-Idreesy、Lars-Oliver Höinck、Johann Lex、Reto Brun

  DOI：10.1016/j.bmcl.2004.11.043

  日期：2005.2

  A remarkable increase in antimalarial in vitro activity was achieved by integration of spiroadamantane motifs in 6-alkylidene 1,2,4-trioxanes 3a-h via diastereoselective photo oxygenation of allylic alcohols and subsequent BF3-catalyzed peroxyacetalization with adamantanone to give the active compounds 3e-h. (C) 2004 Elsevier Ltd. All rights reserved.
• Synthesis of spiroannulated and 3-arylated 1,2,4-trioxanes from mesitylol and methyl 4-hydroxytiglate by photooxygenation and peroxyacetalization
  作者：Axel G Griesbeck、Lars-Oliver Höinck、Jörg M Neudörfl

  DOI：10.3762/bjoc.6.61

  日期：——

  Cycloalkanones were utilized in the Lewis acid catalyzed peroxyacetalization of ß-hydroperoxy homoallylic alcohols (prepared by the ene reaction of the allylic alcohols mesitylol and methyl 4-hydroxytiglate, respectively, with singlet oxygen) to give spiroannulated 1,2,4-trioxanes 5a–5e and 9a–9e, respectively. A second series of 3-arylated trioxanes 10a–10h, that are available from the hydroperoxy alcohol 4 and benzaldehyde derivatives, was investigated by X-ray crystallography.

  环烷酮被用于路易斯酸催化的过氧乙醛化反应，将ß-羟基过氧化异烯丙醇（通过烯烃醇mesitylol和甲基4-羟基丁酸酯与单线态氧反应制备）转化为螺环并联的1,2,4-三噁烷5a–5e和9a–9e。另一系列3-芳基化的三噁烷10a–10h，可由羟基过氧化醇4和苯甲醛衍生物制备，通过X射线晶体学进行了研究。