diethyl (exo,endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: diethyl (exo,endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 英文别名: (+/-)-exo-endo-bis(ethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；diethyl trans-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；diethyl bicyclo[2.2.1]hept-5-ene-(2-endo,3-exo)-dicarboxylate；trans-5-norbornene-2,3-dicarboxylic acid diethyl ester；exo,endo-diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；diethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate；diethyl (1R,2R,3R,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
• 化学式: C₁₃H₁₈O₄
• 分子量: 238.284
• InChiKey: UXRMRBNLTQHPEU-LMLFDSFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  diethyl (exo,endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate 在 lithuim aluminium hydride 作用下， 生成 (-)-2-endo-3-exo-Bis(hydroxymethyl)-bicyclo<2.2.1>hept-5-ene
  参考文献：
  名称：

  Synthesis of Novel Carbocyclic Nucleosides and Pro-Tides Derived from 4-Oxatricyclo[4.2.1.03,7]nonane-9-methanol

  摘要：

  (1R*,2R*,3R*,6R*,7S*)-2-氨基-4-氧杂三环[4.2.1.0^3,7]壬烷-9-甲醇(9)是通过将(1R*,2R*,3R*,4S*)-双环[2.2.1]庚-5-烯-2,3-二甲醇与苄基偶氮甲酸酯处理后再进行氢解制备而成的。氨基化合物9被转化为胸腺嘧啶和嘌呤核苷类似物。制备的类似物通过与甲基N-[氯代(苯氧基)磷酰基]-L-丙氨酸酯在1-甲基咪唑或叔丁基氯化镁存在下进行反应，转化为相应的Pro-Tides。

  DOI：

  10.1135/cccc20071331
• 作为产物：
  描述：

  3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 在 硫酸 、 sodium ethanolate 作用下， 以 乙醇 为溶剂， 生成 diethyl (exo,endo)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate
  参考文献：
  名称：

  Stereospecificity and Concertedness of Retro-Diels-Alder Fragmentation in Some Diester Systems Upon Chemical Ionization

  摘要：

  Retro-Diels-Alder (RDA) fragmentation of cis- and trans-2,3-diethoxycarbonyl-5,6,7,8-dibenzobicyclo[2.2.2]octanes under isobutane and methane chemical ionization conditions is highly stereospecific, giving rise to protonated diethyl maleate and fumarate, respectively. This behaviour indicates a single-step concerted mechanism, analogous to the ground-state RDA process that occurs in neutral molecules in the condensed phase. The analogous dissociation is partially stereospecific in stereoisomeric endo-, exo- and trans-2,3-diethoxycarbonylbicyclo[2.2.1]heptanes and non-stereospecific in endo-, exo- and trans-2,3-diethoxycarbonyl-5,6-benzobicyclo[2.2.2]octanes, indicating the involvement of a stepwise mechanism in the latter two systems. The different behaviour of the above systems is explained in terms of the energy of the RDA fragmentation. The differentiation and quantitative estimates of protonated diethyl maleate and fumarate were obtained from collision-induced dissociation measurements.

  DOI：

  10.1002/(sici)1096-9888(199609)31:9<1028::aid-jms388>3.0.co;2-k

文献信息

• HEPATITIS C VIRUS INHIBITORS AND USES THEREOF IN PREPARATION OF DRUGS
  申请人：CHANGZHOU YINSHENG PHARMACEUTICAL CO., LTD.

  公开号：US20170253614A1

  公开（公告）日：2017-09-07

  A series of hepatitis C virus (HCV) inhibitors and compositions and applications thereof in the preparation of drugs for treating chronic HCV infection. Especially, a series of compounds that are used as NS5A inhibitors, and compositions and uses thereof in the preparations of drugs.

  一系列丙型肝炎病毒（HCV）抑制剂及其组合物，以及在制备用于治疗慢性HCV感染的药物时的应用。特别是一系列用作NS5A抑制剂的化合物，以及在药物制剂中的组合物和用途。
• Diels-Alder reactions using supercritical water as an aqueous solvent medium
  作者：Michael B. Korzenski、Joseph W. Kolis

  DOI：10.1016/s0040-4039(97)01274-4

  日期：1997.8

  A variety of Diels-Alder reactions have been performed in supercritical water as a reaction medium. The rapid reaction of Diels-Alder reactions of cyclopentadiene and various electron poor dienophiles such as diethyl fumarate and acrylonitrile is observed in supercritical water, and leads to high yields of clean products without added catalysts.

  在超临界水中作为反应介质已经进行了多种Diels-Alder反应。在超临界水中观察到了环戊二烯与各种电子贫乏的亲二烯体（如富马酸二乙酯和丙烯腈）的狄尔斯-阿尔德反应的快速反应，可在不添加催化剂的情况下获得高产率的清洁产品。
• How Does Aqueous Solubility of Organic Reactant Affect a Water-Promoted Reaction?
  作者：Yi-Jie Zuo、Jin Qu

  DOI：10.1021/jo500733v

  日期：2014.8.1

  condition, various water-promoted organic reactions can proceed with very high speed. Thus, it is considered that the aqueous solubility of reactant is not an important issue in these reactions. Three types of water-promoted organic reactions were investigated in the current study to distinguish whether the reaction rate of an aqueous reaction was affected by the aqueous solubilities of the reactants. The

  据广泛报道，在“水上”条件下，各种水促进的有机反应可以非常快的速度进行。因此，认为在这些反应中反应物的水溶性不是重要的问题。在当前的研究中，研究了三种类型的水促进的有机反应，以区分水反应的反应速率是否受反应物的水溶解度影响。结果表明，对于在纯净条件下快速进行的Diels-Alder反应，反应物的水溶解度对反应的影响很小。然而，对于在纯条件下缓慢进行的反应，例如[2σ+2σ+2π]环加成反应和环氧化物氨解反应，具有良好水溶性的反应物在水中快速进行。水溶性差的反应物在“水上”条件下反应缓慢或没有反应，因此需要适量的有机助溶剂才能使反应有效。该证据表明，对于这两种类型的反应，都需要将反应物溶解在水中。
• Microwave-Assisted Solvent-Free Diels-Alder Reaction - A Fast and Simple Route to Various 5,6-Substituted Norbornenes and Polychlorinated Norbornenes
  作者：Radim Nencka、Milan Dejmek、Hubert Hřebabecký、Michal Šála、Martin Dračínský

  DOI：10.1055/s-0031-1289610

  日期：2011.12

  Diels-Alder reaction. This procedure proved very versatile, fast, and with an easy workup step, and therefore suitable even for large-scale synthesis. Diels-Alder reactions - bicyclic compounds - cyclo­additions - norbornene - microwave - polychlorinated norbornanes

  通过使用微波辅助的Diels-Alder反应，制备了一系列的5，6-取代的降冰片烯和5，6-取代的多氯降冰片烯。事实证明，该方法非常通用，快速并且具有易于完成的步骤，因此甚至适用于大规模合成。 Diels-Alder反应-双环化合物-环加成-降冰片烯-微波-多氯降冰片烷
• Examining the Effects of Monomer and Catalyst Structure on the Mechanism of Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization
  作者：William J. Wolf、Tzu-Pin Lin、Robert H. Grubbs

  DOI：10.1021/jacs.9b08835

  日期：2019.11.6

  monomer-dependent mechanism for polymerization of norbornene monomers using these fast-initiating catalysts. A series of kinetic experiments, including rate measurements for ROMP, rate measurements for initiation, monomer-dependent kinetic isotope effects, and activation parameters were useful for distinguishing chelating and nonchelating monomers and determining the effect of chelation on the polymerization

  使用一对具有不同空间位阻的 N-杂环卡宾 (NHC) 配体的第三代钌催化剂，详细研究了 Ru 催化的开环复分解聚合 (ROMP) 的机理。聚合物螯合到 Ru 中心的实验证据支持使用这些快速引发催化剂聚合降冰片烯单体的单体依赖性机制。一系列动力学实验，包括 ROMP 的速率测量、引发的速率测量、单体相关动力学同位素效应和活化参数，可用于区分螯合和非螯合单体并确定螯合对聚合机制的影响。螯合金属环的形成是由 NHC 的空间体积和单体的几何形状共同推动的，导致基态稳定，从而减慢聚合速度，并改变了在共聚中传播的 Ru 中心对不同单体的反应性。这里呈现的结果增加了烯烃复分解的机理工作，并可能为 ROMP 催化剂的持续设计提供信息，以获取新的聚合物结构和材料。