cis-(6-methyl-3,6-dihydro-[1,2]dioxin-3-yl)methanol

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: cis-(6-methyl-3,6-dihydro-[1,2]dioxin-3-yl)methanol
• 英文别名: (3,6-dihydro-6-methyl-1,2-dioxin-3-yl)methanol；[(3S,6S)-6-methyl-3,6-dihydro-1,2-dioxin-3-yl]methanol
• 化学式: C₆H₁₀O₃
• 分子量: 130.144
• InChiKey: AWSOGDJVCAULKU-WDSKDSINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  cis-(6-methyl-3,6-dihydro-[1,2]dioxin-3-yl)methanol 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以66%的产率得到(+/-)-[(1aR,2S,5R,5aS)-5-methylperhydrooxireno[2,3-d][1,2]dioxin-2-yl]methanol
  参考文献：
  名称：

  Design of endoperoxides with anti-Candida activity

  摘要：

  Broad antifungal structure-activity relationships governing epoxy-endoperoxides 2 and 3 and their parent endoperoxides I are reported. Their inhibitory activity against Candida albicans in conjunction with hemolytic activity and/or growth inhibition of cultured mammalian cells are reported. This information provided guidance for the further development of endoperoxide and epoxy-endoperoxides as topical antifungal agents. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2006.10.021
• 作为产物：
  描述：

  (2E,4E)-2,4-己二烯-1-醇 在 seco-porphyrazine 作用下， 以 四氯化碳 、 氘代氯仿 为溶剂， 反应 36.0h， 生成 cis-(6-methyl-3,6-dihydro-[1,2]dioxin-3-yl)methanol
  参考文献：
  名称：

  开环易位聚合物球支撑的生态卟啉：高效且可回收的光氧化催化剂

  摘要：

  降冰片烯基标记的二氨基马腈与二丙基马腈的交叉Linstead大环化得到相应的二氨基六丙基卟啉镁，随后将其转化成其锌癸二衍生物。聚合反应产生了相应的ROMPgel和ROMPsphere（ROMP =开环复分解聚合物）试剂，后者被证明是有效的固定化催化剂，用于敏化生产单线态氧，用于纯化最小化的内过氧化物和烯烃加合物的平行合成。

  DOI：

  10.1021/jo052156t

文献信息

• Sustainable photochemistry: solvent-free singlet oxygen-photooxygenation of organic substrates embedded in porphyrin-loaded polystyrene beadsDedicated to Professor Waldemar Adam on the occasion of his 65th birthday and his retirement from the stage of photooxygenation chemistry.
  作者：Axel G. Griesbeck、Anna Bartoschek

  DOI：10.1039/b204017d

  日期：2002.7.11

  A solvent-free photooxygenation process that uses organic substrates embedded in porphyrin-loaded polystyrene beads as solid support is described and applied for ene- and [4+2]-cycloaddition reactions involving singlet oxygen (1Δg).

  描述了一种无溶剂的光氧化过程，该过程使用嵌入铝卟啉负载聚苯乙烯珠的有机底物作为固体支撑，并应用于涉及单态氧 (1Δg) 的烯烃反应和 [4+2] 环加成反应。
• Photooxygenation in Polystyrene Beads with Covalently and Non-Covalently Bound Tetraarylporphyrin Sensitizers
  作者：Axel G. Griesbeck、Tamer T. El-Idreesy、Anna Bartoschek

  DOI：10.1002/adsc.200303181

  日期：2004.2

  synthesized by emulsifier-free emulsion polymerization and directly used for the photooxygenation protocol described above. The latter alternative allows also the use of less polar solvents for the extraction of the oxygenation products from the polymer beads. From the sensitizer loading degree, an optimal substrate/sensitizer molar ratio of 1,000–2,000 was determined and recyclization is possible for at

  描述了两种反应方案，其中涉及使用聚合物载体作为光氧合过程的反应介质：1）使用载有四苯基-（TPP）或四甲苯基卟啉（TTP）的聚苯乙烯珠（PS），其在适当的有机溶剂中会与底物溶胀溶剂，然后在空气中照射。只需将其溶解在酒精溶剂中并过滤，即可分离出产物。2）通过无乳化剂乳液聚合合成聚苯乙烯-二乙烯基苯珠中的共价连接的四苯乙烯基卟啉，并将其直接用于上述的光氧合方案。后一种替代方案还允许使用极性较小的溶剂从聚合物珠粒中提取氧化产物。从敏化剂的负载度来看，最佳的底物/敏化剂摩尔比为1,000–2，4（五个周期后）。两种方法都分别应用于单线态氧与香茅醇（1），区域异构体松烯3和5以及烯丙基醇9a - c的烯反应，以及单线态氧与[4 + 2]-环加成反应山梨醇（7）和手性二烯11。
• 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。
• Polystyrene-supported N-methylthiourea: a convenient new reagent for the hydrogenolysis of bicyclic endoperoxides
  作者：Alan C. Spivey、Carles Giró Mañas、Inderjit Mann

  DOI：10.1039/b508815a

  日期：——

  The single-step preparation of a polystyrene-bound N-methylthiourea and its use for the hydrogenolysis of bicyclic endoperoxides is described.

  描述了聚苯乙烯结合的N-甲基硫脲的一步制备及其在双环内过氧化物氢解中的应用。
• Ring-Opening of Unsymmetrical 1,2-Dioxines Using Cobalt(II) Salen Complexes
  作者：Ben W. Greatrex、Dennis K. Taylor

  DOI：10.1021/jo040241f

  日期：2005.1.1

  The regioselectivity of the metal-catalyzed ring opening of unsymmetrical 1,2-dioxines to cis-γ-hydroxyenones was investigated using two different Co(II) salen complexes. Regioselectivity was determined by direct examination of the enone ratios and by derivitization with a stabilized phosphorus ylide. The steric influence of the substituents on the 1,2-dioxine was the primary influence on regioselectivity

  使用两种不同的Co（II）salen配合物，研究了不对称1,2-二恶英在金属催化的开环中对顺式-γ-羟基烯酮的区域选择性。区域选择性是通过直接检查烯酮比率和通过稳定化的磷酰内酯衍生化来确定的。取代基对1,2-二恶英的空间影响是对区域选择性的主要影响。温度起的作用很小。但是，可以使用溶剂和Co（II）配合物的选择来轻微影响所选底物重排的结果。讨论了反应选择性的起源。