2-[1-Phenyl-meth-(Z)-ylidene]-malonic acid ethyl ester methyl ester | 76386-65-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: 2-[1-Phenyl-meth-(Z)-ylidene]-malonic acid ethyl ester methyl ester
• 英文别名: 1-O-ethyl 3-O-methyl 2-benzylidenepropanedioate
• CAS: 76386-65-7
• 化学式: C₁₃H₁₄O₄
• 分子量: 234.252
• InChiKey: CGMOWHXJCXUMBG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.23
• 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-azidostyrene 、 2-[1-Phenyl-meth-(Z)-ylidene]-malonic acid ethyl ester methyl ester 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 3-ethyl 3-methyl 2,4-diphenyl-4,5-dihydro-3H-pyrrole-3,3-dicarboxylate
  参考文献：
  名称：

  Construction of 1-pyrroline skeletons by Lewis acid-mediated conjugate addition of vinyl azides

  摘要：

  Lewis酸介导的乙烯基叠氮化物与电子亏缺烯烃的共轭加成，有效地构建了1-吡咯烯骨架。

  DOI：

  10.1039/c5cc10299e
• 作为产物：
  描述：

  二氧化碳 、 苯丙炔酸乙酯 、 碘甲烷 在 tris(2,2'-bipyridine)nickel(II) tetrafluoroborate 、 tetrabutylammonium tetrafluoroborate 、 potassium carbonate 、 magnesium 作用下， 生成 2-[1-Phenyl-meth-(Z)-ylidene]-malonic acid ethyl ester methyl ester 、 2-ethoxycarbonyl-3-phenyl-succinic acid dimethyl ester
  参考文献：
  名称：

  From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis

  摘要：

  The incorporation of carbon dioxide into nonactivated alkynes catalyzed by electrogenerated nickel-bipyridine complexes affords alpha,beta-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacycle by magnesium ions is the key step to explain catalysis.

  DOI：

  10.1021/ja00022a037

文献信息

• Expedient radical phosphonylations <i>via</i> ligand to metal charge transfer on bismuth
  作者：Jatin Patra、Akshay M. Nair、Chandra M. R. Volla

  DOI：10.1039/d4sc00692e

  日期：——

  bismuth LMCT catalysis for the generation of heteroatom centered radicals, we hereby report an efficient radical phosphonylation using BiCl3 as the LMCT catalyst. Phosphonyl radicals generated via visible-light induced LMCT of BiCl3 were subjected to a variety of transformations like alkylation, amination, alkynylation and cascade cyclizations. The catalytic system tolerated a wide range of substrate classes

  尽管铋成本低且毒性低，但其在有机合成中的应用有限。尽管Bi( III )盐的光活性已得到充分研究，但尚未在光催化中得到有效利用。迄今为止，只有一份关于铋基光催化的报告，其中使用铋上的配体到金属电荷转移（LMCT）产生以碳为中心的自由基。在这方面，为了扩大铋LMCT催化生成杂原子中心自由基的视野，我们在此报告了使用BiCl 3作为LMCT催化剂的有效自由基膦酰化。通过可见光诱导 BiCl 3的 LMCT 产生的膦酰基自由基经历了各种转化，如烷基化、胺化、炔基化和级联环化。该催化系统可耐受多种底物类别，从而提供出色的支架产率。该反应具有可扩展性，并且需要较低的铋催化负载量。进行了详细的机理研究以探讨反应机理。在当前的工作中，多种自由基磷酸化导致形成 sp 3 -C–P、sp 2 -C–P、sp-C–P 和 P–N 键，这表明铋作为小分子活化的多功能光催化剂的候选资格。
• From stoichiometry to catalysis: electroreductive coupling of alkynes and carbon dioxide with nickel-bipyridine complexes. Magnesium ions as the key for catalysis
  作者：Sylvie Derien、Elisabet Dunach、Jacques Perichon

  DOI：10.1021/ja00022a037

  日期：1991.10

  The incorporation of carbon dioxide into nonactivated alkynes catalyzed by electrogenerated nickel-bipyridine complexes affords alpha,beta-unsaturated acids in moderate to good yields. The electrocarboxylation reaction was undertaken on a preparative scale in the presence of a sacrificial magnesium anode: the formation of acids from alkynes is stoichiometric with respect to the nickel complex if performed in a two-compartment cell but can be made catalytic in a single-compartment cell. An intermediate nickelacycle was isolated from the reaction with 4-octyne. The cleavage of this metallacycle by magnesium ions is the key step to explain catalysis.
• Construction of 1-pyrroline skeletons by Lewis acid-mediated conjugate addition of vinyl azides
  作者：Xu Zhu、Shunsuke Chiba

  DOI：10.1039/c5cc10299e

  日期：——

  The Lewis acid-mediated conjugate addition of vinyl azides to electron-deficient alkenes led to the efficient construction of 1-pyrroline skeletons.

  Lewis酸介导的乙烯基叠氮化物与电子亏缺烯烃的共轭加成，有效地构建了1-吡咯烯骨架。