dimethyl 5-phenyl-4-pentynylmalonate | 147597-80-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: dimethyl 5-phenyl-4-pentynylmalonate
• 英文别名: methyl 2-carbomethoxy-7-phenyl-6-heptynoate；dimethyl 2-(5-phenylpent-4-yn-1-yl)malonate；Dimethyl 2-(5-phenylpent-4-ynyl)propanedioate
• CAS: 147597-80-6
• 化学式: C₁₆H₁₈O₄
• 分子量: 274.317
• InChiKey: SXCZESCISJAYNM-UHFFFAOYSA-N

物化性质

• 沸点：
  368.6±32.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  dimethyl 5-phenyl-4-pentynylmalonate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 四溴化碳 作用下， 以 四氢呋喃 为溶剂， 反应 0.67h， 以79%的产率得到2-bromo-2-(5-phenyl-pent-4-ynyl)malonic acid dimethyl ester
  参考文献：
  名称：

  THF：石墨碳氮化物光催化连续流动自由基环化中的高效电子给体

  摘要：

  发现介孔石墨碳氮化物（mpg-C 3 N 4）是2-溴-1,3-二羰基化合物的金属自由基环化的有效多相光催化剂。导致官能化的环戊烷的反应在温和的条件下进行，可以在连续流动的光反应器中进行。与分批反应相比，使用连续流动反应器可显着减少反应时间（4小时后，批次中0.04 mmol底物的完全转化，而在流动反应器中，相同量的底物可以完全转化）在40分钟内转化为产品）。该反应的机理研究表明，THF不仅起溶剂的作用，而且还是至关重要的氢和电子给体。

  DOI：

  10.1002/chem.201404440
• 作为产物：
  描述：

  (5-chloropent-1-ynyl)benzene 、 丙二酸二甲酯 在 sodium hydride 、 potassium iodide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 paraffin 为溶剂， 以88%的产率得到dimethyl 5-phenyl-4-pentynylmalonate
  参考文献：
  名称：

  Intramolecular and Intermolecular Mn(III)-Induced Carbon Monoxide Trapping Reactions of Alkynes with Malonate and Cyano Ester Units

  摘要：

  Intra- and intermolecular carbon monoxide trapping reactions of alkynes with malonates and cyano esters were developed using a Mn(III)-induced oxidative system. Phenylacetylene was treated with diethyl ethylmalonate in the presence of Mn(OAc)(3) . 2H(2)O, in AcOH-CH3CN (1:1) under carbon monoxide, affording (Z)-4,4-dicarbethoxy-2-phenyl-2-hexenoic acid. Similarly, intramolecular reactions of 4-alkynylmalonates and cyanoacetates proceeded regio- and stereoselectively under the same conditions to afford the corresponding methylenecycloalkanecarboxylic acids in moderate yields. The reaction involves carbon monoxide trapping of vinyl radicals which are formed by the addition of malonate or cyanoacetate radicals induced by Mn(III) to alkynes.

  DOI：

  10.1021/jo9607673

文献信息

• Tandem Pd-Catalyzed Cyclization/Coupling of Non-Terminal Acetylenic Activated Methylenes with (Hetero)Aryl Bromides
  作者：Aleksandra Błocka、Wojciech Chaładaj

  DOI：10.3390/molecules27030630

  日期：——

  methylene compounds to internal alkynes followed by coupling with aryl and heteroaryl bromides. Highly substituted vinylidenecyclopentanes were obtained with good yields, complete selectivity, and excellent functional group tolerance. A plausible mechanism, supported by DFT calculations, involves the oxidative addition of bromoarene to Pd(0), followed by cyclization and reductive elimination. The excellent

  我们报告了一种新方法，用于串联钯催化活性亚甲基化合物与内部炔烃的分子内加成，然后与芳基和杂芳基溴化物偶联。以良好的产率、完全的选择性和优异的官能团耐受性获得了高度取代的亚乙烯基环戊烷。由 DFT 计算支持的一种合理的机制涉及溴芳烃与 Pd(0) 的氧化加成，然后进行环化和还原消除。优异的区域选择性和立体选择性源自底物的烯醇形式与由 π-酸性 Pd(II) 中心激活的炔烃的 5-exo-dig 分子内加成，假定为速率决定步骤。
• Ionic iodocarbocyclization reactions of 4-alkenyl- and 4-alkynylmalonate derivatives
  作者：Osamu Kitagawa、Tadashi Inoue、Keiko Hirano、Takeo Taguchi

  DOI：10.1021/jo00063a033

  日期：1993.5

  The cyclization reactions of dimethyl 4-alkenylmalonate derivatives la-d in the presence Of 12 and Ti(Ot-Bu)4 proceed in a highly regio- and stereocontrolled manner (5-exo cyclization and trans addition) to give (iodoalkyl)cyclopentane derivatives 2 or bicyclic lactones 3 through the displacement of the iodide of 2 by an ester group. Iodocarbocyclization reactions of dimethyl [(cycloalkenyl)alkyl]malonates 1g-i or dimethyl [(methylenecycloalkyl)alkyl]malonates 1j and 1k proceed regio- and stereoselectively to give fused ring compounds or spiro compounds, respectively, as single isomers. Similar reactions of 4-alkynyl derivatives 5 give preferentially E-iodomethylene cyclopentane derivatives 6. An ionic mechanism rather than a radical mechanism is suggested on the basis of the regioselectivity and stereospecificity of the above reactions.