2-hydroperoxy-2-(hydroxymethyl)adamantane | 857494-92-9

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氢过氧化物
• 英文名称: 2-hydroperoxy-2-(hydroxymethyl)adamantane
• 英文别名: (2-Hydroperoxy-2-adamantyl)methanol
• CAS: 857494-92-9
• 化学式: C₁₁H₁₈O₃
• 分子量: 198.262
• InChiKey: DMKDWOKWIVGNKH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-hydroperoxy-2-(hydroxymethyl)adamantane 在 D(+)-10-樟脑磺酸 、 iron(II) bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 30.0h， 生成 (2-hydroxy-2-adamantyl)methyl 6-(4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy)hexanoate
  参考文献：
  名称：

  原型 Dispiro-1,2,4-trioxane 类似物 Dispiro-1,2,4-trioxolane：在与铁反应途径背景下青蒿素的机理比较 (II)

  摘要：

  青蒿素 ( 1 )的 1,2,4-三恶烷杂环的单电子还原形成一级和二级碳中心自由基。的复杂结构1本身不适合于对影响形成和这些碳中心自由基的后续反应的电子和空间影响的满意的清扫。为了帮助区分这些影响，我们表征了非手性双螺-1,2,4-三氧戊环4和双螺-1,2,4-三氧杂环戊烷5 - 7与溴化亚铁和 4-氧代-TEMPO 的反应。我们的结果表明了铁（II）的攻击上的nonketal过氧化物氧原子小的偏好1。对于4，但不是对于5和6，Fe(II) 对受阻较小的过氧化物键氧原子的攻击有强烈的偏好。螺金刚烷在五元三氧杂环戊烷中提供的空间位阻显然比相应的六元三氧杂环己烷大得多。与1 , 5 - 7不同的是，通过熵有利的 β 断裂途径形成相对稳定的 α-氧杂碳中心自由基。这些数据表明，一级或二级碳中心自由基的形成是1和合成过氧化物的抗疟活性的必要但不充分的标准。

  DOI：

  10.1021/jo050385+
• 作为产物：
  描述：

  螺[环氧乙烷-2,2-三环[3.3.1.1~3,7~]癸烷] 在 双氧水 作用下， 以 乙醚 为溶剂， 反应 2.0h， 生成 2-hydroperoxy-2-(hydroxymethyl)adamantane
  参考文献：
  名称：

  二氧化硅硫酸催化合成非对称二螺-1,2,4,5-四恶烷和二螺-1,2,4-三恶烷

  摘要：

  报道了一种由非均相二氧化硅硫酸 (SSA) 催化剂促进的非对称 1,2,4,5-四恶烷和 1,2,4-三恶烷的制备新方案。不同酮类温和条件下反应，与宝石-dihydroperoxides或peroxysilyl醇/β-氢过氧醇以产生良好的产率相应的内过氧化物。我们的机械建议，在分子轨道计算的帮助下，在 ωB97XD/def2-TZVPP/PCM(DCM)//B3LYP/6-31G(d) 理论水平，增强了 SSA 在环缩聚步骤中的作用。这种新方法与以前报道的方法不同，它使用易于获得且价格低廉的试剂，具有可回收的特性，从而为合成新的生物活性内过氧化物建立了一种有效的替代方法。

  DOI：

  10.1021/acs.joc.1c01258

文献信息

• Piperidine dispiro-1,2,4-trioxane analogues
  作者：Sunil Sabbani、Paul A. Stocks、Gemma L. Ellis、Jill Davies、Erik Hedenstrom、Stephen A. Ward、Paul M. O’Neill

  DOI：10.1016/j.bmcl.2008.09.052

  日期：2008.11

  Dispiro N-Boc-protected 1,2,4-trioxane 2 was synthesised via Mo(acac)(2) catalysed perhydrolysis of N-Boc spirooxirane followed by condensation of the resulting beta-hydroperoxy alcohol 10 with 2-adamantanone. N-Boc 1,2,4-trioxane 2 was converted to the amine 1,2,4-trioxane hydrochloride salt 3 which was subsequently used to prepare derivatives (4-7). Several of these novel 1,2,4-trioxanes had nanomolar antimalarial activity versus the 3D7 strain of Plasmodium falciparum. Amine intermediate 3 represents a versatile derivative for the preparation of achiral arrays of trioxane analogues with antimalarial activity. (C) 2008 Elsevier Ltd. All rights reserved.
• Two-Step Synthesis of Achiral Dispiro-1,2,4,5-tetraoxanes with Outstanding Antimalarial Activity, Low Toxicity, and High-Stability Profiles
  作者：Gemma L. Ellis、Richard Amewu、Sunil Sabbani、Paul A. Stocks、Alison Shone、Deborah Stanford、Peter Gibbons、Jill Davies、Livia Vivas、Sarah Charnaud、Emily Bongard、Charlotte Hall、Karen Rimmer、Sonia Lozanom、María Jesús、Domingo Gargallo、Stephen A. Ward、Paul M. O’Neill

  DOI：10.1021/jm701435h

  日期：2008.4.1

  A rapid, two-step synthesis of a range of dispiro-1,2.4,5-tetraoxanes with potent antimalarial activity both in vitro and in vivo has been achieved. These 1,2,4,5-tetraoxanes have been proven to be superior to 1,2,4-trioxolanes in terms of stability and to be superior to trioxane analogues in terms of both stability and activity. Selected analogues have in vitro nanomolar antimalarial activity and good oral activity and are nontoxic in screens for both cytotoxicity and genotoxicity. The synthesis of a fluorescent 7-nitrobenza-2-oxa-1,3-diazole (NBD) tagged tetraoxane probe and use of laser scanning confocal microscopy techniques have shown that tagged molecules accumulate selectively only in parasite infected erythrocytes and that intraparasitic formation of adducts could be inhibited by co-incubation with the iron chelator desferrioxamine (DFO).
• Facile Ring-Opening of Oxiranes by H₂O₂ Catalyzed by Phosphomolybdic Acid
  作者：Yun Li、Hong-Dong Hao、Yikang Wu

  DOI：10.1021/ol900811m

  日期：2009.6.18

  At ambient temperature, in the presence of catalytic amounts of phosphomolybdic acid (PMA), ethereal hydrogen peroxide reacted readily with a range of epoxides, giving corresponding beta-hydroxyhydroperoxides in high yields.
• The activity of dispiro peroxides against Fasciola hepatica
  作者：Xiaofang Wang、Qingjie Zhao、Mireille Vargas、Yuxiang Dong、Kamaraj Sriraghavan、Jennifer Keiser、Jonathan L. Vennerstrom

  DOI：10.1016/j.bmcl.2011.07.024

  日期：2011.9

  Dispiro 1,2,4-trioxanes and 1,2,4,5-tetraoxanes had superior efficacy against Fasciola hepatica than the corresponding ozonides (1,2,4-trioxolanes). For highest efficacy, spiroadamantane and carboxymethyl substructures were required. Three compounds completely cured F. hepatica-infected mice at single oral doses of 50 mg/kg and two were partially curative at single doses of 25 mg/kg. (C) 2011 Elsevier Ltd. All rights reserved.
• Tin(IV) Chloride Promoted Reaction of Oxiranes with Hydrogen Peroxide
  作者：Chunhua Qiao、Xing Yan、Zhongwu Guo

  DOI：10.1055/s-0032-1318213

  日期：——

  A group of substituted oxiranes were readily transformed to the corresponding beta-hydroxyhydroperoxides (HHP) in good yields in ethereal SnCl4-H2O2 system in which SnCl4 acts as catalyst. Alternatively, treating oxiranes with SnCl4 first, followed by addition of ethereal H2O2 solution achieved primary gem-dihydroperoxides (DHP) in moderate yields. In the case of preparing DHP, SnCl4 first promoted the rearrangement of oxiranes to aldehydes, followed by condensation with hydrogen peroxide to provide DHP as final products.