2-methoxycarbonyle oct-6-ynoate de methyle | 137021-58-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-methoxycarbonyle oct-6-ynoate de methyle
• 英文别名: dimethyl 2-(hex-4-yn-1-yl)malonate；Dimethyl 2-hex-4-ynylpropanedioate
• CAS: 137021-58-0
• 化学式: C₁₁H₁₆O₄
• 分子量: 212.246
• InChiKey: PRCVFFAXHWKIPN-UHFFFAOYSA-N

物化性质

• 沸点：
  255.4±30.0 °C(Predicted)
• 密度：
  1.057±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 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：

  2-methoxycarbonyle oct-6-ynoate de methyle 在 calcium hydride 、 [Cu(phen)(PPh₃)2]NO₃ 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.33h， 以58%的产率得到2-Eth-(E)-ylidene-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  高效且通用的微波辅助末端和内部炔烃的铜催化的对苯二酚系留在各种嗜碳亲核试剂上

  摘要：

  本文描述了带有稳定碳亲核试剂的炔烃的高效微波辅助的Conia-ene反应。由市售铜催化剂催化的反应在中性条件下进行，并且通常甚至适用于反应性较低的亲核试剂，如丙二酸酯，氰基乙酸酯和磺酰乙酸酯衍生物。这种铜介导的环异构化也适用于内部未活化的炔烃，仅导致相应的具有E烯烃化学性质的五元产物。

  DOI：

  10.1002/adsc.201000351
• 作为产物：
  描述：

  5-氯戊炔 、 6-氯-2-己炔 在 sodium hydride 、 potassium iodide 作用下， 以61%的产率得到2-methoxycarbonyle oct-6-ynoate de methyle
  参考文献：
  名称：

  Synthese de (e)-arylidene et allylidene cyclopentanes par une annelation catalysee par un complexe de palladium(0)

  摘要：

  When treated with an unsaturated halide in a palladium-catalyzed process, the anions from gamma-acetylenic malonates 4 and 5 stereospecifically lead to cyclopentanes having an exo tri- or tetra-substituted double bond. This reaction which forms simultaneously two carbon-carbon bonds is believed to proceed by nucleophilic attack of the anion on the triple bond activated by the sigma-aryl or sigma-vinyl palladium complex.

  DOI：

  10.1016/s0040-4020(01)86561-3

文献信息

• Tandem Pd-Catalyzed Cyclization/Coupling of Non-Terminal Acetylenic Activated Methylenes with (Hetero)Aryl Bromides
  作者：Aleksandra Błocka、Wojciech Chaładaj

  DOI：10.3390/molecules27030630

  日期：——

  methylene compounds to internal alkynes followed by coupling with aryl and heteroaryl bromides. Highly substituted vinylidenecyclopentanes were obtained with good yields, complete selectivity, and excellent functional group tolerance. A plausible mechanism, supported by DFT calculations, involves the oxidative addition of bromoarene to Pd(0), followed by cyclization and reductive elimination. The excellent

  我们报告了一种新方法，用于串联钯催化活性亚甲基化合物与内部炔烃的分子内加成，然后与芳基和杂芳基溴化物偶联。以良好的产率、完全的选择性和优异的官能团耐受性获得了高度取代的亚乙烯基环戊烷。由 DFT 计算支持的一种合理的机制涉及溴芳烃与 Pd(0) 的氧化加成，然后进行环化和还原消除。优异的区域选择性和立体选择性源自底物的烯醇形式与由 π-酸性 Pd(II) 中心激活的炔烃的 5-exo-dig 分子内加成，假定为速率决定步骤。
• Carbocyclization Reaction of Active Methine Compounds with Unactivated Alkenyl or Alkynyl Groups Mediated by TiCl₄−Et₃N
  作者：Osamu Kitagawa、Takashi Suzuki、Tadashi Inoue、Yoko Watanabe、Takeo Taguchi

  DOI：10.1021/jo981603k

  日期：1998.12.1

  In the presence of TiCl4, Et3N, and I-2, iodocarbocyclization reaction of various active methine compounds having alkenyl groups gave iodocycloalkane derivatives in good yields. On the other hand, TiCl4 and Et3N promote the carbocyclization of active methine compounds with 4-alkynyl groups in the absence of I-2 to give methylenecyclopentane derivatives in good yields. This reaction proceeds with high streoselectivity through a cis-addition of trichlorotitanium enolates of active methine compounds to alkynes, and the resulting vinyltitanium intermediates can be further functionalized by the reaction with various electrophiles.
• Intramolecular carbotitanation reaction of active methine compounds having an unactivated alkyne mediated by TiCl4Et3N
  作者：Osamu Kitagawa、Takashi Suzuki、Tadashi Inoue、Takeo Taguchi

  DOI：10.1016/s0040-4039(98)01579-2

  日期：1998.10

  In the presence of TiCl4 and Et3N, intramolecular carbotitanation reaction of active methine compounds having an unactivated 4-alkynyl group proceeds in a highly cis-selective manner to give methylenecyclopentane derivatives in good yields. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Synthese de (e)-arylidene et allylidene cyclopentanes par une annelation catalysee par un complexe de palladium(0)
  作者：Guy Fournet、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4020(01)86561-3

  日期：1991.8

  When treated with an unsaturated halide in a palladium-catalyzed process, the anions from gamma-acetylenic malonates 4 and 5 stereospecifically lead to cyclopentanes having an exo tri- or tetra-substituted double bond. This reaction which forms simultaneously two carbon-carbon bonds is believed to proceed by nucleophilic attack of the anion on the triple bond activated by the sigma-aryl or sigma-vinyl palladium complex.
• An Efficient and General Microwave-Assisted Copper-Catalyzed Conia-Ene Reaction of Terminal and Internal Alkynes Tethered to a Wide Variety of Carbonucleophiles
  作者：Sonia Montel、Didier Bouyssi、Geneviève Balme

  DOI：10.1002/adsc.201000351

  日期：2010.9.10

  This paper describes a highly efficient, microwave‐assisted, Conia‐ene reaction of alkynes bearing a stabilizing carbon nucleophile. The reaction, catalyzed by a commercially available copper catalyst, proceeds under neutral conditions and is generally applicable even to less reactive nucleophiles such as malonate, cyanoacetate, and sulfonylacetate derivatives. This copper‐mediated cycloisomerization

  本文描述了带有稳定碳亲核试剂的炔烃的高效微波辅助的Conia-ene反应。由市售铜催化剂催化的反应在中性条件下进行，并且通常甚至适用于反应性较低的亲核试剂，如丙二酸酯，氰基乙酸酯和磺酰乙酸酯衍生物。这种铜介导的环异构化也适用于内部未活化的炔烃，仅导致相应的具有E烯烃化学性质的五元产物。