4-(adamantan-2-yl)morpholine | 39234-39-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 恶嗪烷类
• 英文名称: 4-(adamantan-2-yl)morpholine
• 英文别名: 2-morpholinoadamantane；4-adamantan-2-yl-morpholine；2-Morpholino-adamantan；2-Morpholinoadamantan；Adamantane, 2-(4-morpholyl)；4-(2-adamantyl)morpholine
• CAS: 39234-39-4
• 化学式: C₁₄H₂₃NO
• 分子量: 221.343
• InChiKey: YVVBYCGUFRPWSH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  7-[(4-Chlorophenyl)sulfanylmethyl]-7-methylspiro[1,2,4-trioxepane-3,2'-adamantane] 在 2,6-二甲基吡啶 、 三乙酰氧基硼氢化钠 、 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 27.0h， 生成 4-(adamantan-2-yl)morpholine
  参考文献：
  名称：

  Synthesis of 1,2,4-trioxepanes via application of thiol-olefin Co-oxygenation methodology

  摘要：

  Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates beta-hydroxy peroxides that can be condensed in situ with various ketones, to afford a series of functionalised 1,2,4-trioxepanes in good yields. Manipulation of the phenylsulfenyl group in 8a-8c allows for convenient modification to the spiro-trioxepane substituents. Surprisingly, and in contrast to the 1,2,4-trioxanes examined, 1,2,4-trioxepanes are inactive as antimalarials up to 1000 nM and we rationalize this observation based on the inherent stability of these systems to ferrous mediated degradation. FMO calculations clearly show that the sigma* orbital of the peroxide moiety of 1,2,4-trioxane derivatives 4a and 14b are lower in energy and more accessible to attack by Fe(II) compared to their trioxepane analogues 8b and 9b.

  DOI：

  10.1016/j.bmcl.2006.08.098

文献信息

• Hydrogen-free reductive amination using iron pentacarbonyl as a reducing agent
  作者：Oleg I. Afanasyev、Dmitry L. Usanov、Denis Chusov

  DOI：10.1039/c7ob02795h

  日期：——

  We developed solvent-free reductive amination without an external hydrogen source using iron pentacarbonyl as a reducing agent. Neither a catalyst nor any other additives were employed. Various types of substrates are suitable for the reaction, including those with low reactivity, e.g. benzophenone. Among others, the protocol tolerates bromo-, cyano-, benzyloxy-, pyrimidyl and styryl moieties.

  我们使用五羰基铁作为还原剂，开发了无溶剂的无需外部氢源的还原胺化方法。既未使用催化剂也未使用任何其他添加剂。各种类型的底物都适合该反应，包括低反应性的底物，例如二苯甲酮。其中，该方案耐受溴，氰基，苄氧基，嘧啶基和苯乙烯基部分。
• Synthesis, in vitro and in vivo antimalarial assessment of sulfide, sulfone and vinyl amide-substituted 1,2,4-trioxanes prepared via thiol-olefin co-oxygenation (TOCO) of allylic alcohols
  作者：Richard Amewu、Peter Gibbons、Amira Mukhtar、Andrew V. Stachulski、Stephen A. Ward、Charlotte Hall、Karen Rimmer、Jill Davies、Livia Vivas、John Bacsa、Amy E. Mercer、Gemma Nixon、Paul A. Stocks、Paul M. O'Neill

  DOI：10.1039/b924319d

  日期：——

  Thiol-Olefin Co-Oxygenation (TOCO) methodology has been applied to the synthesis of a small library of weak base and polar 1,2,4-trioxanes. The 1,2,4-trioxane units synthesised exhibit remarkable stability as they survive base catalysed hydrolysis and mixed anhydride/amine coupling reactions. This unique stability feature has enabled a range of novel substitution patterns to be incorporated within

  硫醇-烯烃共加氧（合作）方法已应用于弱碱和极性1,2,4-三恶烷的小型文库的合成。这1,2,4-三恶烷 合成的单元在碱催化的水解和混合过程中仍能保持出色的稳定性 酐/胺偶联反应。这种独特的稳定性特征使螺环1,2,4-三恶烷单元中可以结合多种新颖的取代方式。选择类似物表达有力体外在nM抗疟活性，低毒性和口腔活动的恶性疟原虫疟疾的小鼠模型。
• Enhancing the efficiency of the ruthenium catalysts in the reductive amination without an external hydrogen source
  作者：Artemy R. Fatkulin、Oleg I. Afanasyev、Alexey A. Tsygankov、Denis Chusov

  DOI：10.1016/j.jcat.2021.12.018

  日期：2022.1

  Catalytic reductive reactions are essential for laboratory and industrial-scale organic synthesis. However, the nowadays trend is the development of new, more and more complicated reducing systems, which hinders the application of such highly efficient approaches in practice. Another way to achieve the highly active systems is enhancing the activity of the earlier developed catalysts with simple structures

  催化还原反应对于实验室和工业规模的有机合成至关重要。然而，当今的趋势是开发新的、越来越复杂的还原系统，这阻碍了这种高效方法在实践中的应用。实现高活性体系的另一种方法是提高早期开发的具有简单结构的催化剂的活性。在此，我们证明了在向反应混合物中加入碘化物后，钌催化剂在还原胺化中的催化活性显着增加（高达 15 倍）。催化剂周转数高达 9000，产品的制备产率达到了。制定了这种效果的合理原因。
• Sodium hypophosphite mediated reductive amination of carbonyl compounds with <i>N</i>,<i>N</i>-dialkylformamides
  作者：Artemy R. Fatkulin、Vasily Korochantsev、Oleg I. Afanasyev、Evgeniya Podyacheva、Olga Chusova、Dmitry V. Muratov、Maria I. Godovikova、Sergei Semenov、Denis Chusov

  DOI：10.1039/d3nj00728f

  日期：——

  Herein we report a transition-metal- and acid-free protocol for the reductive amination of carbonyl compounds with DMF using a substoichiometric amount of NaH2PO2·H2O. A set of various N,N-dimethylamines were obtained in moderate to excellent yields without chromatographic purification. The general trends and limitations of the method with different formamides as sources of dialkyl-fragments were explored

  在此，我们报告了一种使用亚化学计量的 NaH 2 PO 2 · H 2 O的 DMF 对羰基化合物进行还原胺化的无过渡金属和无酸方案。无需色谱纯化即可获得出色的收率。探讨了使用不同甲酰胺作为二烷基片段来源的方法的一般趋势和局限性。
• Synthesis of 2-adamantyl-containing amines as compounds with potential pharmacological activity
  作者：I. A. Novakov、B. S. Orlinson、E. N. Savel’ev、E. A. Alykova、A. M. Pichugin、M. A. Kovaleva、A. O. Sergeev、N. A. Demidovich、E. V. Kondrat’ev

  DOI：10.1007/s11172-022-3701-1

  日期：2022.12

  The regularities of the reduction of unsaturated nitriles containing the 2-adamantyl fragment with lithium aluminum hydride and nickel—aluminum alloy were studied. In both cases, the double bond and nitrile group were simultaneously reduced. The presence of bulky substituents in the substrate in the α-position to the adamantyl fragment and hydroxy groups significantly retards the process, and the 80–90% yield of the corresponding products is achieved only when the temperature is raised to 65 °C. In the case of using a nickel—aluminum alloy, its 4—6-fold excess is required. The calculation of the potential pharmacological activity of the synthesized compounds shows that they can have antiviral, analgesic, and antidiabetic activity.

  研究了用氢化锂铝和镍铝合金还原含有 2-金刚烷基片段的不饱和腈的规律性。在这两种情况下，双键和腈基同时被还原。底物中金刚烷基片段和羟基的 α 位上存在笨重的取代基会大大延缓这一过程，只有当温度升至 65 ℃ 时，相应产物的产率才能达到 80-90%。如果使用镍铝合金，则需要过量 4-6 倍。对合成化合物潜在药理活性的计算表明，它们具有抗病毒、镇痛和抗糖尿病活性。