2',2'-Diphenylspiro[adamantane-2,3'-oxirane] | 156639-59-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2',2'-Diphenylspiro[adamantane-2,3'-oxirane]
• CAS: 156639-59-7
• 化学式: C₂₃H₂₄O
• 分子量: 316.443
• InChiKey: GAKKSOMQOMVGPY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2',2'-Diphenylspiro[adamantane-2,3'-oxirane] 在 cation-radical orange 9,10-dimethoxy-1,4:5,8-dimethano-1,2,3,4,5,6,7,8-octahydroanthracene*BF₄^(1-) 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以98%的产率得到2-phenyl-2-benzoyladamantane
  参考文献：
  名称：

  Acid Catalysis vs. Electron-Transfer Catalysis via Organic Cations or Cation-Radicals as the Reactive Intermediate. Are These Distinctive Mechanisms?

  摘要：

  Proton transfer to aromatic and olefinic donors (D) lends to the facile interchange of transient carbocations (DH+) and cation-radical (D+.). The same types of cation and cation-radical are reactive intermediates in the acid catalysis and the electron-transfer catalysis of such organic transformations as benzylic coupling, epoxide.-pinacol rearrangements and cis-trans isomerization of stilbenes when they are both carried out under otherwise identical reaction conditions, However, the rapid exchange of diamagnetic cations and paramagnetic cation-radicals blurs the traditional view of sepal ate electrophilic and homolytic processes, and rigorous experimental evidence is required to establish whether acid catalysis and electron-transfer catalysis actually represent distinct mechanistic categories.

  DOI：

  10.3891/acta.chem.scand.52-0114
• 作为产物：
  描述：

  Benzhydrylideneadamantane 在 Fe(AAEMA)3 、 氧气 、 异丁醛 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 6.0h， 生成 2',2'-Diphenylspiro[adamantane-2,3'-oxirane]
  参考文献：
  名称：

  铁（III）的可聚合β-酮酸酯配合物催化受阻烯烃和烯醇醚的好氧环氧化

  摘要：

  在Mukaiyama的条件下，已使用铁（III）催化中心将特殊的受阻烯烃和衍生物进行了环氧化。实验结果可以排除单重态氧和游离过氧酸作为活性物质的参与。

  DOI：

  10.1016/s0040-4039(00)73259-x

文献信息

• Aerobic epoxidation of hindered olefins and enol ethers catalyzed by a polymerizable β-ketoesterate complex of iron(III)
  作者：Luigi Lopez、Piero Mastrorilli、Giuseppe Mele、Cosimo F. Nobile

  DOI：10.1016/s0040-4039(00)73259-x

  日期：1994.5

  Peculiar hindered olefins and derivatives have been epoxidized, under Mukaiyama's conditions, using iron(III) catalytic centres. The experimental results allow to rule out the involvement of singlet oxygen and free peroxyacids as active species.

  在Mukaiyama的条件下，已使用铁（III）催化中心将特殊的受阻烯烃和衍生物进行了环氧化。实验结果可以排除单重态氧和游离过氧酸作为活性物质的参与。
• Catalytic Epoxidation of Hindered Olefins with Dioxygen. Fast Oxygen Atom Transfer to Olefin Cation Radicals from Nitrogen Oxides
  作者：Eric Bosch、Jay K. Kochi

  DOI：10.1021/ja953786n

  日期：1996.1.1

  efficiently converted to epoxides by dioxygen at 25 °C in dichloromethane containing catalytic amounts of nitrogen oxides (NO2, NO+, NO, etc.). Nitrogen dioxide also effects the direct (stoichiometric) epoxidation of the same hindered olefins. Olefin cation radicals are spectrally identified as the first observable intermediate, and separate experiments confirm the facile transfer of an oxygen atom from nitrogen

  受阻烯烃在 25 °C 下通过分子氧在含有催化量氮氧化物（NO2、NO+、NO 等）的二氯甲烷中有效转化为环氧化物。二氧化氮还影响相同受阻烯烃的直接（化学计量）环氧化。烯烃阳离子自由基被光谱鉴定为第一个可观察到的中间体，单独的实验证实氧原子从二氧化氮轻松转移到烯烃阳离子自由基以产生环氧化物。在低温 (-78 °C) 下，添加 1-电子氧化剂如三 (2,4-二溴苯基) 胺阳离子自由基和亚硝 (NO+) 会迅速引发环氧化反应。方案 3 展示了氧化还原变化的完整序列，在受阻烯烃通过阳离子自由基催化转化为环氧化物的过程中，氧化还原变化由氮氧化物介导。
• Lopez Luigi, Mastrorilli Piero, Mele Giuseppe, Nobile Cosimo F., Tetrahedron Lett, 35 (1994) N 21, S 3633-3636
  作者：Lopez Luigi, Mastrorilli Piero, Mele Giuseppe, Nobile Cosimo F.

  DOI：——

  日期：——
• Acid Catalysis vs. Electron-Transfer Catalysis via Organic Cations or Cation-Radicals as the Reactive Intermediate. Are These Distinctive Mechanisms?
  作者：Rajendra Rathore、Jay K. Kochi、Augusto Canavesi、Larry L. Miller、Giovanni V. Sebastiani、George W. Francis、József Szúnyog、Bengt Långström

  DOI：10.3891/acta.chem.scand.52-0114

  日期：——

  Proton transfer to aromatic and olefinic donors (D) lends to the facile interchange of transient carbocations (DH+) and cation-radical (D+.). The same types of cation and cation-radical are reactive intermediates in the acid catalysis and the electron-transfer catalysis of such organic transformations as benzylic coupling, epoxide.-pinacol rearrangements and cis-trans isomerization of stilbenes when they are both carried out under otherwise identical reaction conditions, However, the rapid exchange of diamagnetic cations and paramagnetic cation-radicals blurs the traditional view of sepal ate electrophilic and homolytic processes, and rigorous experimental evidence is required to establish whether acid catalysis and electron-transfer catalysis actually represent distinct mechanistic categories.
• Aerobic oxidations of unsaturated substrates under mukaiyama's conditions: The role of the metal and of the sacrificial aldehyde
  作者：Piero Mastrorilli、Cosimo F. Nobile、Gian P. Suranna、Luigi Lopez

  DOI：10.1016/0040-4020(95)00410-a

  日期：1995.7

  Aerobic epoxidation of unsaturated substrates has been achieved under Mukaiyama's conditions (atmospheric pressure of dioxygen, in the presence of an excess of sacrificial aldehyde) with or without metal catalyst. The influence of light in non-catalysed reactions and the possible role of the aldehyde and of the metal complex in catalysed reactions are discussed. Two mechanistic pathways are proposed for Co(II) and Fe(III) [Ni(II)] catalytic centres.