1,1-diethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate | 158389-19-6

• 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: 1,1-diethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate
• 英文别名: 3-vinylcyclopent-3-ene-1,1-dicarboxylic acid diethyl ester；diethyl 3-vinylcyclopent-3-ene-1,1-dicarboxylate；3-ethenyl-3-cyclopentene-1,1-dicarboxylic acid diethyl ester；Diethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate
• CAS: 158389-19-6
• 化学式: C₁₃H₁₈O₄
• 分子量: 238.284
• InChiKey: BQUXXIGIZGQOSH-UHFFFAOYSA-N

物化性质

• 沸点：
  286.8±30.0 °C(Predicted)
• 密度：
  1.148±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  1,1-diethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 14.0h， 生成 4,4-[bis(benzyloxy)methyl]-1-vinylcyclopentene
  参考文献：
  名称：

  Hydrovinylation of 1,3-Dienes:  A New Protocol, an Asymmetric Variation, and a Potential Solution to the Exocyclic Side Chain Stereochemistry Problem

  摘要：

  Cyclic and acyclic 1,3-dienes undergo efficient (substrate/catalyst = 72) heterodimerization with ethylene in the presence of a Ni catalyst prepared from [o-(PhCH2O)]C6H4PPh2, [(allyl)2NiBr]2, and Na+ BAr4- (Ar = 3,5-bis-trifluromethylphenyl), giving 1,2-addition products. Yields up to 99% can be realized for several 1-vinylcycloalkenes and 1-substituted 1,3-butadienes. Phospholanes with suitably placed hemilabile ligating groups and phosphoramidites derived from binaphthol are excellent ligands for an asymmetric variation of this reaction, the latter giving 99% yield and >95% ee's for selected substrates. An example of how an exocyclic chiral center can be used to install other stereo-centers in the ring (e. g., the carbon to which the side chain is attached) is also provided. These discoveries open an expeditious entry into several biologically relevant classes of compounds, especially those carrying tetrahydronaphthalene and related heterocyclic moieties.

  DOI：

  10.1021/ja0561338
• 作为产物：
  描述：

  烯丙基丙二酸二乙酯 在 Ph₃PAuNTf₂ 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷-D2 、 mineral oil 为溶剂， 反应 3.0h， 生成 1,1-diethyl 3-ethenylcyclopent-3-ene-1,1-dicarboxylate
  参考文献：
  名称：

  金 (I) 催化中的限制诱导选择性——使用大体积三-(邻-联芳基)膦配体的好处

  摘要：

  合成了一系列带有庞大的三-(邻-联芳基)膦配体的金(I) 配合物。它们表现出显着的催化活性，从而证明了它们作为有机化学合成工具的价值。

  DOI：

  10.1002/anie.202203452

文献信息

• Design and Synthesis of Angularly Annulated Spirocyclics via Enyne Metathesis and the Diels–Alder Reaction as Key Steps
  作者：Sambasivarao Kotha、Rashid Ali、Arti Tiwari

  DOI：10.1055/s-0034-1378280

  日期：——

  developed a simple and an efficient route to a range of angularly fused spirocycles by the application of enyne metathesis and the Diels–Alder reaction as key steps. The enyne metathesis protocol has been further extended to the dibenzylation of indane-1,3-dione by using cross-enyne metathesis in the presence of hexa-1,5-diene with the aid of Grubbs’ 1st generation catalyst followed by an aromatization

  摘要 通过应用烯炔复分解和Diels-Alder反应作为关键步骤，我们已经开发出了一种简单而有效的途径，可用于一系列有角度融合的螺环。借助Grubbs的第一代催化剂，在hexa-1,5-diene存在下使用交叉烯炔复分解，将烯炔复分解方案进一步扩展至茚满1,3-二酮的二苄基化反应。与DDQ。 通过应用烯炔复分解和Diels-Alder反应作为关键步骤，我们已经开发出了一种简单而有效的途径，可用于一系列有角度融合的螺环。借助Grubbs的第一代催化剂，在hexa-1,5-diene存在下使用交叉烯炔复分解，将烯炔复分解方案进一步扩展至茚满1,3-二酮的二苄基化反应。与DDQ。
• Evaluation of the Electronic Properties of a Carbodiphosphorane through Gold Catalysis
  作者：Ahmad El-Hellani、Christophe Bour、Vincent Gandon

  DOI：10.1002/adsc.201100287

  日期：2011.8

  Carbodiphosphoranes [C(PR3)2] are divalent carbon(0) derivatives which can be used as ligands to form either MC(PR3)2 or (M)2 C(PR3)2 species. They were computationally predicted to be even stronger electron donors than N-heterocyclic carbenes. We have introduced hexaphenylcarbodiphosphorane [C(PPh3)2] for the first time in gold catalysis in order to validate this prediction by experimentation. Its

  碳二膦酸酯[C（PR 3）2 ]是二价碳（0）衍生物，可用作配体以形成MC（PR 3）2或（M）2 C（PR 3）2物种。通过计算预测，它们比N-杂环卡宾具有更强的电子供体。为了在实验中验证这一预测，我们在金催化中首次引入了六苯基碳二磷烷[C（PPh 3）2 ]。其单和digold复合物相比，三（2,4-二-叔-代表性的金（I）催化转化中的亚磷酸-丁基苯基）亚磷酸酯，三苯基膦和1,3-双（2,6-二异丙基苯基）咪唑-2-亚烷基。讨论了这些配体的优缺点。
• Ruthenium-Indenylidene Olefin Metathesis Catalyst with Enhanced Thermal Stability
  作者：Anzhelika Kabro、Thierry Roisnel、Cédric Fischmeister、Christian Bruneau

  DOI：10.1002/chem.201001659

  日期：2010.10.25

  crystallography. Complex 10 displays a very high thermal stability with a half life of six days at 110 °C in [D8]toluene. Complex 10 was evaluated in various ring‐closing metathesis reactions and ring‐opening metathesis polymerization of dicyclopentadiene, in which it showed a latent behavior with low activity at room temperature and high activity upon thermal activation.

  两个新的钌络合物轴承二齿（κ 2 ö，Ç）异丙氧基茚基配体和PPH 3（9）或PCY 3（10中，Cy =环己基）配位体已被合成，并通过完全表征1 H和13 C NMR光谱学和X射线晶体学。络合物10在[D 8 ]甲苯中在110°C下显示出非常高的热稳定性，半衰期为6天。复杂10 在双环戊二烯的各种开环易位反应和开环易位聚合反应中对苯甲酸进行了评估，结果表明该化合物具有潜在的行为，在室温下具有较低的活性，而在热活化后具有较高的活性。
• Pentiptycene-based concave NHC–metal complexes
  作者：Roman Savka、Sabine Foro、Herbert Plenio

  DOI：10.1039/c6dt01724j

  日期：——

  N-Heterocyclic carbenes with two pentiptycene units and metal complexes with Cu, Ag, Au and Ir were synthesized with the metal center residing at the bottom of the concave ligand.

  具有两个pentiptycene单元的N-杂环卡宾和金属配合物与Cu、Ag、Au和Ir的金属中心位于凹面配体底部处被合成。
• Anion Chelation via Double Chalcogen Bonding: The Case of a Bis-telluronium Dication and Its Application in Electrophilic Catalysis via Metal–Chloride Bond Activation
  作者：Benyu Zhou、François P. Gabbaï

  DOI：10.1021/jacs.1c04482

  日期：2021.6.16

  to engage their counteranions via secondary interactions. Yet, this property has rarely been exploited for anion binding. Motivated by such an application, we have now synthesized a bis-telluronium dication ([3]2+) that was obtained as a tetrafluoroborate salt by reaction of 2,7-di-tert-butyl-9,9-dimethylxanthene-4,5-diboronic acid with phenoxatellurine difluoride and BF3·OEt2. As confirmed by the formation

  人们早就知道碲阳离子通过二次相互作用与它们的反阴离子结合。然而，这种特性很少被用于阴离子结合。受此类应用的启发，我们现在合成了一种双碲二阳离子 ([ 3 ] 2+ )，它是通过 2,7-二叔丁基-9,9-二甲基氧杂蒽-4的反应获得的四氟硼酸盐， 5-二硼酸与二氟化苯氧苯胺和BF 3 ·OEt 2。[ 3 ][BF 4 ] 2 , [ 3 ] 2+结构中Te-(μ-BF 4 )-Te桥的形成证实了这一点作为对阴离子的双齿路易斯酸。[ 3 ][BF 4 ] 2也被转换成更暴露的[ 3 ][BArF 24 ] 2 ([BArF 24 ] − = [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] - )。后者易于电离 Ph 3 CCl，其氯阴离子结合常数比单功能模型化合物高出近 4 个数量级。这种新的双碲二阳离子的独特性质因其激活 Ph 3 的能力而进一步突出PAuCl和顺式-(Ph 3