5-methoxycarbonyl-5-prop-2-ynylhex-2-enedioic acid dimethyl ester | 121497-81-2

• 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: 5-methoxycarbonyl-5-prop-2-ynylhex-2-enedioic acid dimethyl ester
• 英文别名: trimethyl (E)-hept-1-en-6-yne-1,4,4-tricarboxylate
• CAS: 121497-81-2
• 化学式: C₁₃H₁₆O₆
• 分子量: 268.266
• InChiKey: RRKRZOUUUYZANQ-VOTSOKGWSA-N

物化性质

• 沸点：
  349.5±42.0 °C(Predicted)
• 密度：
  1.161±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  78.9
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5-methoxycarbonyl-5-prop-2-ynylhex-2-enedioic acid dimethyl ester 在 bis-triphenylphosphine-palladium(II) chloride 、 bis(1,5-cyclooctadiene)nickel (0) 、 copper(l) iodide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 40.0 ℃ 、101.33 kPa 条件下， 反应 7.0h， 生成 3-(Carboxy-methoxycarbonyl-methyl)-4-[1-phenyl-meth-(E)-ylidene]-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  在二氧化碳气氛下镍介导的烯炔环化

  摘要：

  研究了镍介导的α，ω-烯炔的羧化反应。在化学计量的零价镍络合物的存在下，在烯烃上具有吸电子基团的炔烃通过分子内环化与二氧化碳反应，以高收率得到环状羧酸。通过该羧基化环化方案制备了各种杂环化合物。该反应似乎通过α，ω-烯炔部分的氧化环加成至零价镍络合物，二氧化碳在Csp 3-镍键上的区域选择性插入以及所得氧杂环丙烷环中间体的水解而进行。

  DOI：

  10.1016/j.tet.2006.03.121

文献信息

• Fischer carbene-mediated conversions of enynes to bi- and tricyclic cyclopropane-containing carbon skeletons
  作者：Paul F. Korkowski、Thomas R. Hoye、David B. Rydberg

  DOI：10.1021/ja00216a066

  日期：1988.4

  Reactions de divers composes aliphatiques enyniques avec le complexe carbonyle du methoxy-1 ethylidene chrome pour donner divers composes bicycliques et monocycliques

  反应 de divers 组成 aliphatiques enyniques avec le complexe carbonyle du methoxy-1 ethylidene chrome pour donner divers 组成 bicycliques et monocycliques
• Hoye, Thomas R.; Suriano, Joseph A., Journal of the American Chemical Society, 1993, vol. 115, # 3, p. 1154 - 1156
  作者：Hoye, Thomas R.、Suriano, Joseph A.

  DOI：——

  日期：——
• Pd-Catalyzed Cycloisomerization to 1,2-Dialkylidenecycloalkanes. 2. Alternative Catalyst System
  作者：Barry M. Trost、Donna L. Romero、Frode Rise

  DOI：10.1021/ja00089a016

  日期：1994.5

  The mechanisms by which palladium complexes may catalyze the cycloisomerization of 1,6- and 1,7-enynes to dialkylidenecycloalkanes were probed by exploring a catalyst system different than a ligated palladium acetate which previously has proven to be successful. Although carboxylic acids showed no discernible interaction with palladium(0) complexes, this combination proved to be a powerful catalyst system to effect this cycloisomerization. The fact that the two catalyst systems do not have the same reactivity profile suggests this new catalyst system may operate by a different mechanism. Evidence supporting a pathway invoking formation of a hydridopalladium acetate followed by hydropalladation as initiation is presented. Steric and electronic effects direct the regioselectivity of the termination step to form either 1,3- or 1,4-diene products. The 1,3-diene products participate exceedingly well in Diels-Alder reactions, both inter- and intramolecularly. The presence of an oxygen substituent at the position allylic to the diene served as both a regiochemical control element for the palladium-catalyzed cycloisomerization and a diastereochemical control element for the Diels-Alder reaction. The net result of these two steps, the first of which is a catalyzed isomerization and the second an addition, is a highly efficient approach to complex polycycles in terms of both selectivity and atom economy.
• Novel Alkenylative Cyclization Using a Ruthenium Catalyst
  作者：Miwako Mori、Nozomi Saito、Daisuke Tanaka、Masanori Takimoto、Yoshihiro Sato

  DOI：10.1021/ja029747a

  日期：2003.5.1

  Novel alkenylative cyclization of enyne was developed using Cp*RuCl(cod) under ethylene gas at room temperature.
• Further studies on palladium-catalyzed bismetallative cyclization of enynes in the presence of Bu3SnSiMe3
  作者：Yoshihiro Sato、Noriko Imakuni、Tomohiro Hirose、Hideaki Wakamatsu、Miwako Mori

  DOI：10.1016/s0022-328x(03)00601-6

  日期：2003.12

  Bismetallative cyclization of enynes with Bu3SnSiMe3 catalyzed by Pd(0) complex was realized for the first time, which gives cyclized products containing a vinylsilane moiety and a homoallyltin moiety in good yield. In this cyclization, Pd-2(dba)(3)(CHCl3)-C-. or Pd(OH)2 on charcoal is effective as a Pd(0) catalyst and the addition of a phosphine ligand increased the formation of alkyne bismetallation by-product. On the other hand, it was found that a nucleophilic N-heterocyclic carbene could be utilized as a ligand for this cyclization. The utility of the cyclized products obtained from this cyclization in synthetic organic chemistry have been proven by transformation into cyclopropanol derivatives. (C) 2003 Elsevier B.V. All rights reserved.