dimethyl 3-(1-phenylvinyl)cyclopent-3-ene-1,1-dicarboxylate | 1380876-06-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: dimethyl 3-(1-phenylvinyl)cyclopent-3-ene-1,1-dicarboxylate
• 英文别名: 1,1-dimethyl 3-(1-phenylvinyl)cyclopent-3-ene-1,1-dicarboxylate；Dimethyl 3-(1-phenylethenyl)cyclopent-3-ene-1,1-dicarboxylate
• CAS: 1380876-06-1
• 化学式: C₁₇H₁₈O₄
• 分子量: 286.328
• InChiKey: SPBUYZVVERQXGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  烯丙基-(3-苯基-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 72.0h， 以81%的产率得到dimethyl 3-(1-phenylvinyl)cyclopent-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

• The role of cyclobutenes in gold(i)-catalysed skeletal rearrangement of 1,6-enynes
  作者：Ana Escribano-Cuesta、Patricia Pérez-Galán、Elena Herrero-Gómez、Masaki Sekine、Ataualpa A. C. Braga、Feliu Maseras、Antonio M. Echavarren

  DOI：10.1039/c2ob25419k

  日期：——

  electron-donating substituents at the alkyne undergo gold(I)-catalysed single cleavage skeletal rearrangement, whereas substrates with electron-withdrawing substituents evolve selectively to double cleavage rearrangement. Theoretical calculations provide a qualitative rationale for these effects, and suggest that bicyclo[3.2.0]hept-5-enes are involved as intermediates. We provide the first X-ray structural evidence

  在炔烃上带有给电子取代基的1，6-烯炔经历金（I）催化的单裂解骨架重排，而具有吸电子取代基的底物选择性地演化为双裂解重排。理论计算为这些作用提供了定性的理论依据，并暗示涉及双环[3.2.0]庚-5-烯作为中间体。我们提供了第一个X射线结构证据，证明该类产物在1,6-烯炔的环异构化中的形成。