2-methyl-5-norbornene-2-carboxaldehyde

• 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: 2-methyl-5-norbornene-2-carboxaldehyde
• 英文别名: (1S,4S)-2-methylbicyclo[2.2.1]hept-5-ene-2-carbaldehyde
• 化学式: C₉H₁₂O
• 分子量: 136.194
• InChiKey: OEUNHSRWYZGUDW-ZQTLJVIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-methyl-5-norbornene-2-carboxaldehyde 在 氢氧化钾 、 一水合肼 作用下， 以 乙二醇 为溶剂， 生成 (1S)-5,5-dimethylbicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  在一些5取代的降冰片2烯中加成硫醇

  摘要：

  硫醇与5-取代的降冰片烯-2-烯衍生物反应，通过跨双键加成而提供2- exo-和3- exo-硫化物。产物的比例似乎取决于分别在位置2和3处进攻形成的中间自由基的相对稳定性，以及苯硫醇的添加，还取决于在位置2和3处自由基进攻的可逆性变化。硫醇与Norborn-2-en-5-one形成2- exo-，3- exo-和7-抗硫化物，最后一个起源于在位置2处由自由基进攻形成的中间体的重排或通过攻击第2位形成非经典的均烯化自由基。

  DOI：

  10.1039/p19730000433
• 作为产物：
  描述：

  2-甲基丙烯醛 、 环戊二烯 在 K-10 montmorillonite 1-hexyl-3-methylimidazolium tetrafluoroborate 作用下， 反应 1.0h， 以95%的产率得到2-methyl-5-norbornene-2-carboxaldehyde
  参考文献：
  名称：

  Enhanced Diels–Alder reactions: on the role of mineral catalysts and microwave irradiation in ionic liquids as recyclable media

  摘要：

  This manuscript explores in detail the combined effect of solid supports or microwave irradiation in ionic liquids on a series of Diels-Alder reactions involving 1,3-cyclopentadiene and numerous dienophiles. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2007.01.031

文献信息

• Toward a mild dehydroformylation using base-metal catalysis
  作者：Dylan J. Abrams、Julian G. West、Erik J. Sorensen

  DOI：10.1039/c6sc04607j

  日期：——

  biosynthesis of cholesterol and related sterols under mild conditions using base-metal catalysts. In contrast, chemists have recently developed a non-oxidative dehydroformylation method; however, it requires high temperatures and a precious-metal catalyst. Careful study of both approaches has informed our efforts to design a base-metal catalyzed, mild dehydroformylation method that incorporates benefits from

  脱氢甲酰化或醛类反应生成烯烃，氢气和一氧化碳的反应是一种有力的转化，尽管逆反应加氢甲酰化在工业上具有很高的重要性，但这种转化仍未开发。有趣的是，大自然通常在使用贱金属催化剂的温和条件下，在胆固醇和相关固醇的生物合成中进行相关的转化，即氧化脱氢甲酰化。相反，化学家们最近开发了一种非氧化脱氢甲酰化方法。但是，它需要高温和贵金属催化剂。对这两种方法的仔细研究使我们努力设计一种贱金属催化的轻度脱氢甲酰化方法，该方法综合了每种方法的优点，同时避免了它们各自的缺点。重要的，
• Dilithium 2,2′-methylenebis(4,6-di-tert-butylphenoxide) as a bidentate Lewis acid in organic synthesis
  作者：Takashi Ooi、Akira Saito、Keiji Maruoka

  DOI：10.1016/s0040-4039(98)00575-9

  日期：1998.5

  Dilithium 2,2'-methylenebis(4,6-di-tert-butylphenoxide) can be successfully utilized as a bidentate Lewis acid for simultaneous coordination to carbonyl groups, thereby accelerating the Diels-Alder reactions. The double activation ability of the bidentate lithium reagent toward carbonyls is emphasized in comparison with the corresponding monodentate lithium reagent. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Enantioselective Synthesis of Cyclothiazide Analogues:  Novel Probes of the Stereospecific Actions of Benzothiadiazines at AMPA-Type Glutamate Receptors
  作者：Yuefei Hu、Kelvin A. Yamada、David K. Chalmers、Durga P. Annavajjula、Douglas F. Covey

  DOI：10.1021/ja9525317

  日期：1996.1.1

  The stereospecific interactions of the eight stereoisomers of dihydromethylcyclothiazide, an analogue of cyclothiazide, with AMPA-type glutamate receptors was investigated using electrophysiological methods that measured the ability of each stereoisomer to inhibit AMPA receptor desensitization. The eight stereoisomers were obtained by HPLC separation of four pairs of enantiomerically pure (>95% ee) diastereomers prepared from (1R-exo)-, (1R-endo)-, (1S-exo)-, and (1S-endo)-2-methylbicyclo[2.2.1]heptane-2-carboxaldehyde intermediates. The desensitization process was blocked most potently by [1S-[1 alpha,2 alpha(R*),4 alpha]]-dihydromethylcyclothiazide, one of the stereoisomers prepared from the (1S-endo)-carboxaldehyde. The smallest effects on the desensitization process were found for the four stereoisomers prepared from the (1R-exo)- and (1R-endo)-carboxaldehydes. Significant differences in the ability to inhibit desensitization were observed between all diastereomer pairs except those prepared from the (1S-exo)-carboxaldehyde.
• Addition of thiols to some 5-substituted norborn-2-enes
  作者：D. I. Davies、D. J. A. Pearce、E. C. Dart

  DOI：10.1039/p19730000433

  日期：——

  Thiols react with 5-substituted norborn-2-ene derivatives to afford 2-exo- and 3-exo-sulphides by addition across the double bond. Product proportions appear to depend on the relative stability of the intermediate radicals formed by attack at positions 2 and 3 respectively, and, in additions of benzenethiol, also on the variation in the degree of reversibility of radical attack at positions 2 and 3

  硫醇与5-取代的降冰片烯-2-烯衍生物反应，通过跨双键加成而提供2- exo-和3- exo-硫化物。产物的比例似乎取决于分别在位置2和3处进攻形成的中间自由基的相对稳定性，以及苯硫醇的添加，还取决于在位置2和3处自由基进攻的可逆性变化。硫醇与Norborn-2-en-5-one形成2- exo-，3- exo-和7-抗硫化物，最后一个起源于在位置2处由自由基进攻形成的中间体的重排或通过攻击第2位形成非经典的均烯化自由基。
• Enhanced Diels–Alder reactions: on the role of mineral catalysts and microwave irradiation in ionic liquids as recyclable media
  作者：Ignacio López、Guadalupe Silvero、María José Arévalo、Reyes Babiano、Juan Carlos Palacios、José Luis Bravo

  DOI：10.1016/j.tet.2007.01.031

  日期：2007.3

  This manuscript explores in detail the combined effect of solid supports or microwave irradiation in ionic liquids on a series of Diels-Alder reactions involving 1,3-cyclopentadiene and numerous dienophiles. (c) 2007 Elsevier Ltd. All rights reserved.