dimethyl 3-vinylcyclopent-3-ene-1,1-dicarboxylate

• 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 3-vinylcyclopent-3-ene-1,1-dicarboxylate
• 英文别名: Dimethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate；dimethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate
• 化学式: C₁₁H₁₄O₄
• 分子量: 210.23
• InChiKey: PQXCWIHMZLPGAX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  乙烯 、 dimethyl 3-vinylcyclopent-3-ene-1,1-dicarboxylate 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 (Z)-dimethyl 3-ethylidene-4-vinylcyclopentane-1,1-dicarboxylate
  参考文献：
  名称：

  Ruthenium-catalyzed tandem enyne metathesis/hydrovinylation

  摘要：

  原位改性Grubbs第一代复分解催化剂可以实现一种串联的烯炔复分解/水解乙烯化反应，且与已知的钌催化水解乙烯化反应的区位选择性互补。

  DOI：

  10.1039/c0cc00008f
• 作为产物：
  描述：

  2-烯丙基-2-(2-丙炔基)丙二酸二乙酯 在 1.2 molpercent gold nanoparticles supported on TiO₂ 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 28.0h， 以94%的产率得到dimethyl 3-vinylcyclopent-3-ene-1,1-dicarboxylate
  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

• Ruthenium catalyzed enyne cycloisomerizations and hydroxycyclizations with skeletal rearrangement
  作者：J.W. Faller、Philip P. Fontaine

  DOI：10.1016/j.jorganchem.2006.01.009

  日期：2006.4

  A neutral arene-tethered ruthenium complex was found to be a catalyst precursor for enyne cycloisomerizations and hydroxycyclizations. The observed products were the result of a skeletal rearrangement process, and include an unusual cyclization to form a six-membered ring. Labeling studies on the six-membered ring product are in accord with an electrophilic activation mechanism that proceeds via cationic

  发现中性的芳烃系的钌络合物是烯炔环异构化和羟基环化的催化剂前体。观察到的产物是骨骼重排过程的结果，并且包括不寻常的环化以形成六元环。对六元环产物的标记研究符合通过阳离子环丙基卡宾中间体进行的亲电活化机理。
• A Simple and Effective Co-Catalyst for Ring-Closing Enyne Metathesis Using Grubbs I type Catalysts: A Practical Alternative to “Mori’s Conditions”
  作者：Guy C. Lloyd-Jones、Alan J. Robinson、Laurent Lefort、Johannes G. de Vries

  DOI：10.1002/chem.201001510

  日期：2010.8.16

  “Catch‐and‐release”: Simple alk‐1‐enes are effective at liberating buta‐1,3‐dienes from vinyl alkylidene ruthenium complexes, as well as undergoing alkene–alkylidene exchange with enyne substrates to regenerate the alk‐1‐ene. This ability to “catch‐and‐release” ruthenium alkylidenes allows alk‐1‐enes higher than ethylene (“Mori's conditions”) to be used as a co‐catalysts in terminal enyne metathesis with the Grubbs

  “捕集并释放”：简单的烯-1-烯可有效地从乙烯基亚烷基钌络合物中释放丁烯-1,3-二烯，以及与烯炔基质进行烯-亚烷基交换以再生烯-1-烯。这种“捕捉并释放”钌烷基亚烷基的能力使得比乙烯高的烯烃1-烯（“莫里条件”）可与第一代Grubbs配合物一起用作末端烯炔复分解的助催化剂（L = PCy 3））。
• Silica‐Supported Phosphine–Gold Complexes as an Efficient Catalytic System for a Dearomative Spirocyclization
  作者：Zhen Cao、Antoine Scalabre、Sylvain Nlate、Sonia Buffière、Reiko Oda、Emilie Pouget、Brigitte Bibal

  DOI：10.1002/chem.202004251

  日期：2021.1.4

  combination of metal catalyst and inorganic silica frameworks provides a greener approach to recyclable catalysis. In this study, three phosphine–gold chloride complexes have been successfully covalently grafted onto chiral silica nanohelices. The resulting 3D ensembles showed chiroptical properties that allowed the monitoring of the supported ligands. The heterogeneous gold chloride catalysts in cooperation

  金属催化剂和无机二氧化硅骨架的结合提供了一种更环保的可循环催化方法。在这项研究中，已成功将三种膦-氯化金复合物共价接枝到手性二氧化硅纳米螺旋上。所得的3D集成体显示出整脊特性，可以监控所支持的配体。与三氟甲磺酸银配合使用的非均相氯化金催化剂在各种反应中表现出高反应性，尤其是在芳基炔酸酯的螺环化中，可以使用0.05mol％的催化负载量。该多相催化剂可以容易地回收和再循环七或八次，而没有任何效率损失。通过添加更多的三氟甲磺酸银，
• Gold(I)-Catalyzed Cyclizations of 1,6-Enynes: Alkoxycyclizations andexo/endo Skeletal Rearrangements
  作者：Cristina Nieto-Oberhuber、M. Paz Muñoz、Salomé López、Eloísa Jiménez-Núñez、Cristina Nevado、Elena Herrero-Gómez、Mihai Raducan、Antonio M. Echavarren

  DOI：10.1002/chem.200501088

  日期：2006.2.8

  Gold(I) complexes are the most active catalysts for alkoxy- or hydroxycyclization and for skeletal rearrangement reactions of 1,6-enynes. Intramolecular alkoxycyclizations also proceed efficiently in the presence of gold(I) catalysts. The first examples of the skeletal rearrangement of enynes by the endocyclic cyclization pathway are also documented. Iron(III) is also able to catalyze exo and endo

  金（I）配合物是最有效的催化剂，用于烷氧基或羟基环化以及1,6-炔烃的骨架重排反应。在金（I）催化剂的存在下，分子内烷氧基环化也有效地进行。还记录了环内环化途径引起的炔烃骨架重排的第一个例子。铁（III）还能够催化1,6-烯炔的外切和内切骨架重排，尽管这种转化的范围更为有限。金（I）催化的环内环化反应的机理不同于在PdII，HgII或RhI催化剂存在下的机理。
• A Stiboranyl Platinum Triflate Complex as an Electrophilic Catalyst
  作者：Di You、Jesse E. Smith、Srobona Sen、François P. Gabbaï

  DOI：10.1021/acs.organomet.0c00193

  日期：2020.12.14

  ([(o-(R2P)C6H4)2SbCl2]PtCl (R = Ph, iPr)) with 3 equiv of AgOTf. The crystal structures of 2 and 4 confirmed that the chloride ligands have been fully substituted by more labile triflate ligands. Despite structural similarities in the dinuclear cores of 2 and 4, only 2 acts as a potent carbophilic catalyst in enyne cyclization reactions. The high activity of 2 is also reflected by its ability to promote

  与显影电后过渡金属催化剂的视图，我们现在已合成[（ø - （PH 2 P）C ^ 6 ħ 4）2的Sb（OTF）2 ]的Pt（OTF）（2）和[（ø - （i Pr 2 P）C 6 H 4）2 Sb（OTf）2 ] Pt（OTf）（4）通过处理相应的三氯化物（[（o-（R 2 P）C 6 H 4）2 SbCl 2 ] PtCl（R = Ph，iPr））与3当量的AgOTf。2和4的晶体结构证实氯化物配体已被更不稳定的三氟甲磺酸酯配体完全取代。尽管2和4的双核核心在结构上相似，但只有2个在烯炔环化反应中充当有效的嗜碳催化剂。的高活性2也通过其促进加成吡咯和噻吩衍生物，以炔能力反射。结构和计算分析表明2的出色反应性来自有利的空间效应和电子效应。最后比较2使用先前报道的自活化催化剂[（o-（Ph 2 P）C 6 H 4）2 Sb（OTf）2 ] PtCl强调了三氟甲磺酸盐对氯取代的好处。