diethyl 3-vinylcyclohex-3-ene-1,1-dicarboxylate | 173949-55-8

• 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: diethyl 3-vinylcyclohex-3-ene-1,1-dicarboxylate
• 英文别名: 3-Cyclohexene-1,1-dicarboxylic acid, 3-ethenyl-, diethyl ester；diethyl 3-ethenylcyclohex-3-ene-1,1-dicarboxylate
• CAS: 173949-55-8
• 化学式: C₁₄H₂₀O₄
• 分子量: 252.31
• InChiKey: SNUYDPWGQIVVMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  diethyl 3-vinylcyclohex-3-ene-1,1-dicarboxylate 在 三羰基(萘)铬 、 氢气 作用下， 以 四氢呋喃 为溶剂， 45.0~50.0 ℃ 、4.05 MPa 条件下， 反应 3.0h， 以93%的产率得到diethyl (E)-3-ethylidenecyclohexane-1,1-dicarboxylate
  参考文献：
  名称：

  分子内烯烃 - 炔烃复分解和 1,4-顺式氢化作为具有环外双键化合物的立体控制途径

  摘要：

  (but-3-en-1-yl)(propargyl)丙二酸二乙酯的分子内烯烃-炔烃复分解得到3-乙烯基环己-3-烯-1,1-二羧酸二乙酯，其共轭二烯体系在η6-(萘)三羰基铬的存在。由此形成的 3-亚乙基环己烷-1,1-二羧酸二乙酯的环外双键严格为 (E)-构型。

  DOI：

  10.1007/s11172-020-2739-1
• 作为产物：
  描述：

  diethyl (but-3-en-1-yl)(propargyl)malonate 在 Grubbs catalyst first generation 、 乙烯 作用下， 以 二氯甲烷 为溶剂， 反应 90.0h， 以92%的产率得到diethyl 3-vinylcyclohex-3-ene-1,1-dicarboxylate
  参考文献：
  名称：

  分子内烯烃 - 炔烃复分解和 1,4-顺式氢化作为具有环外双键化合物的立体控制途径

  摘要：

  (but-3-en-1-yl)(propargyl)丙二酸二乙酯的分子内烯烃-炔烃复分解得到3-乙烯基环己-3-烯-1,1-二羧酸二乙酯，其共轭二烯体系在η6-(萘)三羰基铬的存在。由此形成的 3-亚乙基环己烷-1,1-二羧酸二乙酯的环外双键严格为 (E)-构型。

  DOI：

  10.1007/s11172-020-2739-1

文献信息

• Remarkable Effect of Ethylene Gas in the Intramolecular Enyne Metathesis of Terminal Alkynes
  作者：Miwako Mori、Norikazu Sakakibara、Atsushi Kinoshita

  DOI：10.1021/jo980896e

  日期：1998.9.1
• Initiators of the Type Mo(NAr)(CHR‘)(OR‘ ‘)₂ for the Controlled Polymerization of Diethyldipropargylmalonate
  作者：Jennifer Adamchuk、Richard R. Schrock、Zachary J. Tonzetich、Peter Müller

  DOI：10.1021/om060029x

  日期：2006.4.1

  The reaction between Mo(NAr)(trans-CHCH=CHMe)[OCMe(CF3)(2)](2)(quin) (Ar = 2,6-i-Pr-2-C6H3; quin quinuclidine) and lithium tert-butoxide yields Mo(NAr)(trans-CHCH=CHMe)(O-t-BU)(2)(quin) (1). The achiral,syn isomer could be isolated and was shown in an X-ray study to be a trigonal bipyramid in which quinuclidine is coordinated trans to a syn butenylidene group. A base-free species (2) that contains a five-membered ring as part of a trienylidene unit could be obtained by treating Mo(NAr)(CHCMe2R)-[OCMe(CF3)(2)](2) (R = Me, Ph) with diethyl 3-(2-methylprop-1-enyt)-4-vinylcyclopent-3-ene-1,1-dicarboxylate (B) in pentane. The tert-butoxide analogue of 2 (3) was obtained straightforwardly and was shown in an X-ray study to be the syn alkylidene isomer. The reaction between 1-methylidene-5,5-bis(carboxyethyl)cyclohex-1-ene and Mo(NAr)(CHCMe3)[OCMe(CF3)(2)](2) gave Mo(NAr)[1-methylidene-5,5-bis(carboxyethyl)cyclohex-1-ene)] [OCMe(CF3)(2)](2) (5a), which could be treated with LiO-t-Bu to yield an analogous tert-butoxide species (5b). An X-ray structure of a sample of 5b that retained 2 equiv of LiOCMe(CF3)(2) showed it to be a dimeric species in which two Mo complexes were joined through a Li4O4 heterocubane-type structure binding to one ester oxygen in each of the Mo species. Reactions between diethyldipropargylmalonate (DEDPM) and 1, 3, or 5b showed initiation to be smooth with k(p)/k(i) values less than 1 and to yield oligomers that were consistent with formation of polymers that contain largely five-membered rings. All reactions can be followed by proton NMR spectra of the alkylidene proton region, and all appear to be living polymerizations under the conditions employed. A Wittig-like reaction between diethyl 3-formyl-4-(2-methylprop-1-enyl)cyclopent-3-ene-1, 1-dicarboxylate (A) and 2 yielded a symmetric pentaene (C) as an ivory-colored solid. The heptaene (D) and the nonaene (E) could be isolated from reactions between 1 equiv of DEDPM and 3 in CH2Cl2 in the presence of I equiv of quinuclidine at -30 degrees C followed by quenching with aldehyde A.
• Intramolecular alkene–alkyne metathesis and 1,4-cis-hydrogenation as a stereocontrolled route to compounds with exocyclic double bonds
  作者：A. A. Vasil’ev、L. Engman、E. P. Serebryakov

  DOI：10.1007/s11172-020-2739-1

  日期：2020.1

  Intramolecular alkene-alkyne metathesis of diethyl (but-3-en-1-yl)(propargyl)malonate affords diethyl 3-vinylcyclohex-3-ene-1,1-dicarboxylate whose conjugated diene system was 1,4-cis-hydrogenated in the presence of η6-(naphthalene)chromium tricarbonyl. The exocyclic double bond of thus formed diethyl 3-ethylidenecyclohexane-1,1-dicarboxylate is strictly (E)-configured.

  (but-3-en-1-yl)(propargyl)丙二酸二乙酯的分子内烯烃-炔烃复分解得到3-乙烯基环己-3-烯-1,1-二羧酸二乙酯，其共轭二烯体系在η6-(萘)三羰基铬的存在。由此形成的 3-亚乙基环己烷-1,1-二羧酸二乙酯的环外双键严格为 (E)-构型。
• Confinement‐Induced Selectivities in Gold(I) Catalysis—The Benefit of Using Bulky Tri‐( <i>ortho</i> ‐biaryl)phosphine Ligands
  作者：Karim Muratov、Fabien Gagosz

  DOI：10.1002/anie.202203452

  日期：2022.7.11

  A series of gold(I) complexes bearing bulky tri-(ortho-biaryl)phosphine ligands were synthesized. They were shown to exhibit remarkable catalytic activities thus demonstrating their value as synthetic tools in organic chemistry.

  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。