3-(2-丙烯基)-环戊烯-1,1-二羧酸二乙酯 | 100747-45-3

• 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
• 中文名称: 3-(2-丙烯基)-环戊烯-1,1-二羧酸二乙酯
• 英文名称: Dicarbomethoxy-4,4 isopropenyl-1 cyclopentene
• 英文别名: 3-(2-propenyl)-cyclopentene-1,1-dicarboxylic acid diethyl ester；dimethyl 3-(prop-1-en-2-yl)cyclopent-3-ene-1,1-dicarboxylate；Dimethyl 3-prop-1-en-2-ylcyclopent-3-ene-1,1-dicarboxylate
• CAS: 100747-45-3
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: FQFAJIGNGZUVML-UHFFFAOYSA-N

物化性质

• 沸点：
  271.9±30.0 °C(Predicted)
• 密度：
  1.125±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  diethyl 7-octen-2-yne-5,5-dicarboxylate 在 1.2 molpercent gold nanoparticles supported on TiO₂ 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 96.0h， 以92%的产率得到3-(2-丙烯基)-环戊烯-1,1-二羧酸二乙酯
  参考文献：
  名称：

  Cyclization of 1,6-Enynes Catalyzed by Gold Nanoparticles Supported on TiO₂: Significant Changes in Selectivity and Mechanism, as Compared to Homogeneous Au-Catalysis

  摘要：

  Gold nanoparticles supported on TiO2 (1.2 mol %) catalyze, for the first time under heterogeneous conditions, the cycloisomerization of a series of 1,6-enynes in high yields. In several cases, the product selectivity differs significantly as compared to homogeneous Au(I)-catalysis. Based on product analysis and stereoisotopic studies it is proposed that the major or exclusive pathway involves a 5-exo cyclization mode to form stereoselectively gold cyclopropyl carbenes that undergo a single cleavage pathway, in contrast to homogeneous Au-catalysis where the double cleavage pathway operates substantially.

  DOI：

  10.1021/ol301212j

文献信息

• DFT and Experimental Exploration of the Mechanism of InCl₃-Catalyzed Type II Cycloisomerization of 1,6-Enynes: Identifying InCl₂⁺ as the Catalytic Species and Answering Why Nonconjugated Dienes Are Generated
  作者：Lian-Gang Zhuo、Ji-Ji Zhang、Zhi-Xiang Yu

  DOI：10.1021/jo301471w

  日期：2012.10.5

  Finally InCl2+ cation coordination assisted nonconjugated [1,2]-hydride shifts deliver the final nonconjugated diene products. The preference of generating nonconjugated dienes instead of conjugated dienes in the cycloisomerization reaction is mainly due to two reasons: coordination of the InCl2+ to the alkene part in [1,2]-H shift transition states disfavors the conjugated [1,2]-H shifts that generate

  InCl 3和其他In（III）物种已被广泛用作许多反应的催化剂。但是，这些反应的真正催化种类是什么？通过DFT计算和InCl 3催化的1,6-烯炔（此处讨论的所有1,6-烯炔均为烯内部炔烃分子）的环异构化反应的机理和区域选择性的实验研究，我们提出了该化合物的催化物种反应是原位生成的InCl 2 +。进一步的电喷雾电离高分辨率质谱（ESI-HRMS）支持了乙腈溶液中InCl 2 +的存在。InCl 2 +的发现因为催化物种表明由In（III）物种催化的其他反应也可能具有阳离子In（III）物种作为真正的催化剂。DFT计算表明，由InCl 3催化的1，6-烯炔的环异构化的催化循环从InCl 2 +配位到底物的炔烃开始，产生乙烯基阳离子。然后，乙烯基阳离子与基质的烯基部分进行非经典环丙烷化反应，得到均聚物阳离子，然后进行新的均聚物阳离子重排，涉及到[1,3]碳转移，从而获得更稳定的均聚物阳离子15。最后是InCl
• Carbopalladation of β-allenylmalonates : a way to cyclopentenyl or vinylcyclopropyl derivatives.
  作者：Mohammed Ahmar、Bernard Cazes、Jacques Gore

  DOI：10.1016/s0040-4039(00)89253-9

  日期：1985.1
• Formation de derives cyclopenteniques et vinylcyclopropaniques lors de la carbopalladation de diesters et d' α-sulfonylesters alleniques
  作者：Mohammed Ahmar、Bernard Cazes、Jacques Gore

  DOI：10.1016/s0040-4020(01)81636-7

  日期：1987.1
• AHMAR, MOHAMMED;CAZES, BERNARD;GORE, JACQUES, TETRAHEDRON, 43,(1987) N 15, 3453-3463
  作者：AHMAR, MOHAMMED、CAZES, BERNARD、GORE, JACQUES

  DOI：——

  日期：——
• Cyclization of 1,6-Enynes Catalyzed by Gold Nanoparticles Supported on TiO₂: Significant Changes in Selectivity and Mechanism, as Compared to Homogeneous Au-Catalysis
  作者：Charis Gryparis、Christina Efe、Christos Raptis、Ioannis N. Lykakis、Manolis Stratakis

  DOI：10.1021/ol301212j

  日期：2012.6.15

  Gold nanoparticles supported on TiO2 (1.2 mol %) catalyze, for the first time under heterogeneous conditions, the cycloisomerization of a series of 1,6-enynes in high yields. In several cases, the product selectivity differs significantly as compared to homogeneous Au(I)-catalysis. Based on product analysis and stereoisotopic studies it is proposed that the major or exclusive pathway involves a 5-exo cyclization mode to form stereoselectively gold cyclopropyl carbenes that undergo a single cleavage pathway, in contrast to homogeneous Au-catalysis where the double cleavage pathway operates substantially.