dimethyl endo,endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylate | 4545-84-0

• 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: dimethyl endo,endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylate
• 英文别名: dimethyl (1S,2R,3S,4R)-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate
• CAS: 4545-84-0
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: FPRGHVZMTXXTRC-YNFQOJQRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  dimethyl endo,endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 22.0h， 生成 dimethyl bicyclo<2,2,2>oct-5-ene-endo-2,exo-3-dicarboxylate
  参考文献：
  名称：

  Carman, Raymond M.; Smith, Stephanie S., Australian Journal of Chemistry, 1981, vol. 34, # 6, p. 1285 - 1294

  摘要：

  DOI：
• 作为产物：
  描述：

  甲醇 、 meso-endo-tetrahydro-4,7-ethanoisobenzofuran-1,3-dione 在 盐酸 作用下， 生成 dimethyl endo,endo-bicyclo<2.2.2>oct-5-ene-2,3-dicarboxylate
  参考文献：
  名称：

  Additions of Group 6A and 7A electrophilic reagents to dimethyl endo,endo-bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylate: Competitive formation of .gamma.- and .delta.-lactones

  摘要：

  DOI：

  10.1021/jo01293a016

文献信息

• Carboxylates Stacked over Aromatic Rings Promote Salt Bridge Formation in Water
  作者：Samuel E. Thompson、David B. Smithrud

  DOI：10.1021/ja011973h

  日期：2002.1.1

  having an aromatic ring were able to form a salt bridge in water. Although most of the obvious interactions, such as ionic and cation-pi, and ion desolvation are important factors, association of an amino acid in water required the presence of the entire amino acid. This result suggests that the interaction between the aliphatic portion of an amino acid and an aromatic ring of a template is an important

  在蛋白质 X 射线晶体结构中观察到的几个盐桥显示出一致的羧酸盐模式，位于芳环表面附近，与配体的精氨酸残基形成键。为了确定这些复合物的驱动力，对含有 N-乙酰精氨酸甲酯、N-乙酰赖氨酸甲酯、氯化胍或 KCl 和一系列二酸的一个成员的溶液进行了 (1) H NMR 或电位结合滴定模板，它们的羧酸盐下方具有芳香族或脂肪族基团。只有具有芳香环的模板才能在水中形成盐桥。尽管大多数明显的相互作用，例如离子和阳离子-pi，以及离子去溶剂化是重要因素，但氨基酸在水中的结合需要整个氨基酸的存在。该结果表明氨基酸的脂肪族部分与模板的芳香环之间的相互作用是络合的重要组成部分。芳香族模板还将 N-乙酰精氨酸甲酯从水中运输到 1-辛醇。运输研究的结果根据可能降低蛋白质折叠的一些激活障碍的潜在中间状态进行了讨论。
• OXYMERCURATION OF Δ⁵-[2,2,2]-BICYCLOÖCTENE
  作者：D. D. K. Chiu、George F Wright

  DOI：10.1139/v59-209

  日期：1959.9.1

  It has now been shown that an earlier assignment of configuration in which 1,4-↑↑-ethylene-Δ⁵-cyclohexenedicarboxylic acids and their derivatives were presumed to form with mercuric salts 5-↓-hydroxy-6-↓-anionomercuri-1,4-↑↑-ethylenecyclohexanedicarboxylic acid derivatives is incorrect. Instead 5-↓-hydroxy-6-↑-anionomercuri-1,4-↑↑-ethylenecyclohexanedicarboxylic acid derivatives are formed, similarly with the homologous 5-↓-hydroxy-6-↑-anionomercuri-1,4-methylenecyclohexane-2,3-dicarboxylic acid derivatives. This similarity is exemplified by comparable dipole moments. The exception is 5-↓-hydroxy-6-↓-chloromercuri-1,4-↑↑-methylenecyclohexane-2,3-↓↓-dicarboxylic acid, γ-lactone, which has a configuration opposite to all of the others of these series having boat-type cyclohexane ring conformations. The exception is attributed to steric effects.

  现在已经显示，先前假定1,4-↑↑-乙烯-Δ⁵-环己烯二羧酸及其衍生物与汞盐形成5-↓-羟基-6-↓-阴离子汞基-1,4-↑↑-乙烯环己二羧酸衍生物的构型是错误的。相反，形成了5-↓-羟基-6-↑-阴离子汞基-1,4-↑↑-乙烯环己二羧酸衍生物，类似于同系物5-↓-羟基-6-↑-阴离子汞基-1,4-亚甲基环己烷-2,3-二羧酸衍生物。这种相似性通过可比的偶极矩来加以说明。例外是5-↓-羟基-6-↓-氯汞基-1,4-↑↑-亚甲基环己烷-2,3-↓↓-二羧酸，γ-内酯，其构型与这个系列中所有其他具有船型环己烷环构象的物质相反。这个例外归因于立体效应。
• 1,3-Dipolar Cycloadditions to Bicyclic Olefins. IV. The Influence of Non-neighboring Double Bonds on the Stereoselectivity in 1,3-Dipolar Cycloadditions to Bicyclo[<i>n</i>.2.2]alkadienes
  作者：Hisaji Taniguchi、Toshikazu Ikeda、Eiji Imoto

  DOI：10.1246/bcsj.51.1495

  日期：1978.5

  3-bis(methoxycarbonyl)bicyclo[2.2.2]octa-2,5-diene (5) to afford only endo adducts. The cycloadditions of these 1,3-dipoles to the more electron-rich double bond of 6,7-bis(methoxycarbonyl)bicyclo[3.2.2]nona-6,8-diene (6) give only exo adducts. Benzonitrile-N-phenylimine (4) undergoes cycloadditions to both the more electron-rich and the more electron-poor double bonds of 5 or 6. The reaction of 4 with 5 yields

  1,3-偶极子，例如苯乙醛腈氧化物 (1)、苯甲腈氧化物和苯基叠氮化物，会与 2,3-双（甲氧基羰基）双环 [2.2.2]octa-2 的更富电子双键发生环加成反应， 5-二烯 (5) 仅提供内加合物。这些 1,3-偶极子与 6,7-双（甲氧基羰基）双环 [3.2.2] 壬 -6,8-二烯 (6) 的更富电子双键的环加成仅产生外加合物。苯甲腈-N-苯基亚胺 (4) 与 5 或 6 的富电子双键和缺电子双键发生环加成反应。 4 与 5 的反应产生两个内加合物，4 与 6 的反应产生两个外加合物。然而，1 到 5,6-endo,endo-双（甲氧基羰基）双环 [2.2.2]oct-2-ene 的环加成得到外加和内加合物。
• Role of steric, electrostatic and hydrogen bonding effects as face selectivity controlling factors in nitrone cycloadditions
  作者：Marina Burdisso、Remo Gandolfi、Paolo Pevarello、Augusto Rastelli

  DOI：10.1016/s0040-4039(00)95332-2

  日期：1987.1

  A highly selective -attack is promoted by hydrogen bonding effects in the reaction of nitrones with -5-hydroxybicyclo[2.2.2]oct-2-enes. By contrast repulsive interactions (steric and electrostatic) between other kinds of substituents and the attacking nitrone result in an almost exclusive selectivity.

  在硝酮与-5-羟基双环[2.2.2]辛-2-烯的反应中，氢键作用促进了高度选择性的攻击。相比之下，其他种类的取代基与攻击性硝酮之间的排斥性相互作用（空间和静电）导致几乎排他的选择性。
• Two directions of heterocyclization in the reactions of dimethyl bicyclo[2.2.2]oct-5-ene-endo-2,endo-3-dicarboxylate with hetarenesulfenyl chlorides
  作者：A. V. Borisov、V. K. Osmanov、G. N. Borisova、Zh. V. Matsulevich、G. K. Fukin

  DOI：10.1007/s11172-018-2105-8

  日期：2018.3

  A reaction of dimethyl bicyclo[2.2.2]oct-5-ene-endo-2,endo-3-dicarboxylate with 1,3-benzо- thiazole-2- and 3-methoxycarbonylpyridine-2-sulfenyl chlorides leads to two types of heterocyclization products, which are formed through the ring closure by the oxygen atom of the carbоmethoxy group and/or by the nitrogen atom of the hetaryl fragment of the sulfenylating agent. The product ratio is affected

  二甲基双环[2.2.2] oct-5-ene-endo-2,endo-3-dicarboxylate 与 1,3-benzо-thiazole-2- 和 3-methoxycarbonylpyridine-2-sulfenyl 氯化物的反应导致两种类型的杂环化产物，由碳甲氧基的氧原子和/或亚磺酰化剂的杂芳基片段的氮原子通过闭环形成。产品比例受亚磺酰氯的介质性质和结构特征的影响。