5-endo-cyanobicyclo<2.2.2>oct-2-ene

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 5-endo-cyanobicyclo<2.2.2>oct-2-ene
• 英文别名: endo-5-Cyanobicyclo<2.2.2>oct-2-ene；(+/-)-bicyclo[2.2.2]oct-5-ene-2endo-carbonitrile；(+/-)-Bicyclo[2.2.2]oct-5-en-2endo-carbonitril；(1R,2R,4R)-bicyclo[2.2.2]oct-5-ene-2-carbonitrile
• 化学式: C₉H₁₁N
• 分子量: 133.193
• InChiKey: WFLYMJQGWKVLTO-VGMNWLOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  5-endo-cyanobicyclo<2.2.2>oct-2-ene 在 氢氧化钾 、 sodium hydroxide 、 水 、 碘 、 碳酸氢钠 作用下， 生成 endo-5-hydroxy-exo-6-iodo-endo-3-carboxybicyclo<2.2.2>octane-γ-lactone
  参考文献：
  名称：

  Stereochemistry of Diels-Alder Adducts. II. The Alkylation of Some Bicyclic Nitriles

  摘要：

  DOI：

  10.1021/ja01553a044
• 作为产物：
  描述：

  bicyclo[2.2.2]oct-5-ene-2-carbonyl chloride 在 氨 、 phosphorus pentoxide 作用下， 生成 5-endo-cyanobicyclo<2.2.2>oct-2-ene
  参考文献：
  名称：

  Stereochemistry of Diels-Alder Adducts. II. The Alkylation of Some Bicyclic Nitriles

  摘要：

  DOI：

  10.1021/ja01553a044

文献信息

• Orbital Unsymmetrization of Olefins Arising from Non-equivalent Orbital Interactions. .SIGMA.-.PI. Coupling in Bicyclo(2.2.2)octenes.
  作者：Tomohiko OHWADA、Masanobu UCHIYAMA、Motonori TSUJI、Iwao OKAMOTO、Koichi SHUDO

  DOI：10.1248/cpb.44.296

  日期：——

  We characterized experimentally the substituent effect of a 5-exo substituent on the π facial selectivities of bicyclo[2.2.2]octenes toward electrophilic oxidative reactions such as epoxidation and dihydroxylation, and we discuss the underlying orbital interactions of vicinal σ orbitals and the olefinic π orbital involved in bicyclo[2.2.2]octenes, and commonly in methylenenorbornanes. Of significance is the out-of-phase motif of these σ-π couplings. Electron-withdrawing substituents such as cyano and carboxylic acid groups unequalize the relevant σ-π coupling, leading to the observed syn-facial preference. Alkyl substituents exhibit an electron-donative perturbing effect, depending on the bicyclic ring system.

  我们通过实验表征了 5-exo 取代基对双环[2.2.2]辛烯对环氧化和二羟基化等亲电氧化反应的 π 面选择性的影响，并讨论了邻位 σ 轨道和烯属 π 的潜在轨道相互作用。轨道涉及双环[2.2.2]辛烯，并且常见于亚甲基降冰片烷。重要的是这些 σ-π 耦合的异相基序。吸电子取代基（例如氰基和羧酸基团）使相关的 σ-π 耦合不均衡，导致观察到的顺面偏好。烷基取代基表现出给电子扰动效应，具体取决于双环系统。
• The influence of captodative effect on the dienophilicity of olefins. The easy diels-alder reaction of α-methylthioacrylonitrile with cyclohexadiene
  作者：Jean-Luc Boucher、Lucien Stella

  DOI：10.1016/s0040-4039(01)80848-0

  日期：1985.1

  We show that the cycloaddition of α-methylthioacrylonitrile to cyclohexadiene is faster than that of acrylonitrile. This indicates that the captodative substitution exerts an accelerating effect on the Diels-Alder reaction despite the larger steric bulk of the methylthio group compared to hydrogen.

  我们表明，α-甲基硫代丙烯腈向环己二烯的环加成比丙烯腈的环加成更快。这表明尽管甲硫基的空间体积比氢大，但Capoddative取代对Diels-Alder反应起加速作用。
• Evidence for 2-hexene-1,6-diyl diradicals accompanying the concerted Diels-Alder cycloaddition of acrylonitrile with nonpolar 1,3-dienes
  作者：Yufei Li、Anne Buyle Padias、H. K. Hall

  DOI：10.1021/jo00077a025

  日期：1993.12

  The spontaneous reactions of a series of alkyl 1,3-dienes with acrylonitrile (AN) were investigated. Reproducible spontaneous copolymerizations were shown to compete with the expected concerted [4 + 2] cycloadditions. For dienes which exist in s-cis/s-trans equilibrium, both copolymer and cycloadduct are formed. Kinetic measurements show that the alternating copolymerization and cycloaddition are two independent parallel second order reactions. With 1,3-cyclohexadiene and 1,2-dimethylenecyclohexane, for which s-gauche is in equilibrium with s-cis, copolymerization still competes with cycloaddition. The s-trans-locked verbenene forms only copolymer, while s-cis-locked cyclopentadiene and 1,2-dimethylenecyclopentane form only cycloadduct rapidly. Our explanation involves a 2-hexene- 1,6-diradical, formed by combination between the terminal carbons of the s-gauche or s-trans diene and acrylonitrile. This does not cyclize but initiates copolymerization. Competitively s-cis conformer undergoes classical concerted [4 + 2] addition.
• Alder et al., Chemische Berichte, 1958, vol. 91, p. 1516,1523
  作者：Alder et al.

  DOI：——

  日期：——
• Alder et al., Chemische Berichte, 1955, vol. 88, p. 144,153
  作者：Alder et al.

  DOI：——

  日期：——