(3Z,3aSR,6aRS)-diethyl 3,3a,6,6a-tetrahydro-3-(4-oxopentylidene)pentalene-1,1(2H)dicarboxylate

• 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: (3Z,3aSR,6aRS)-diethyl 3,3a,6,6a-tetrahydro-3-(4-oxopentylidene)pentalene-1,1(2H)dicarboxylate
• 英文别名: diethyl (3Z,3aS,6aR)-3-(4-oxopentylidene)-2,3a,6,6a-tetrahydropentalene-1,1-dicarboxylate
• 化学式: C₁₉H₂₆O₅
• 分子量: 334.412
• InChiKey: FBLLOFFARBEKQE-KUKCEQTMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  丁烯酮 、 diethyl cyclopent-2-en-1-yl(prop-2-yn-1-yl)propanedioate 在 三乙胺 bis(triphenylphosphine)nickel(II) chloride 、 zinc(II) chloride 、 锌 作用下， 以 乙腈 为溶剂， 反应 6.0h， 以44%的产率得到(3Z,3aSR,6aRS)-diethyl 3,3a,6,6a-tetrahydro-3-(4-oxopentylidene)pentalene-1,1(2H)dicarboxylate
  参考文献：
  名称：

  Ni-Catalyzed, ZnCl₂-Assisted Domino Coupling of Enones, Alkynes, and Alkenes

  摘要：

  A Ni(O)/ZnCl2 system effectively promotes the coupling of enones and alkene-tethered alkynes. In the reaction with 1,6-enynes, the oxidative cyclization of Ni(O) species on enones across the alkyne part followed by ZnCl2-promoted cleavage generates alkenylnickel intermediates. Subsequent migratory insertion of the tethered alkene occurs with 5-exo-cyclization. When the resulting sigma-alkylnickel intermediates have beta-hydrogen atoms, the reaction terminates by beta-hydrogen elimination to provide cyclopentane derivatives. On the other hand, a sigma-alkylnickel intermediate that does not have beta-hydrogen atoms undergoes the insertion of a second alkene unit to cause a domino effect via a three-fold C-C bond formation process with and without the cleavage of one C-C bond.

  DOI：

  10.1021/ja047580a

文献信息

• Ni-Catalyzed, ZnCl₂-Assisted Domino Coupling of Enones, Alkynes, and Alkenes
  作者：Shin-ichi Ikeda、Reiko Sanuki、Hiroko Miyachi、Hitoshi Miyashita、Masami Taniguchi、Kazunori Odashima

  DOI：10.1021/ja047580a

  日期：2004.8.1

  A Ni(O)/ZnCl2 system effectively promotes the coupling of enones and alkene-tethered alkynes. In the reaction with 1,6-enynes, the oxidative cyclization of Ni(O) species on enones across the alkyne part followed by ZnCl2-promoted cleavage generates alkenylnickel intermediates. Subsequent migratory insertion of the tethered alkene occurs with 5-exo-cyclization. When the resulting sigma-alkylnickel intermediates have beta-hydrogen atoms, the reaction terminates by beta-hydrogen elimination to provide cyclopentane derivatives. On the other hand, a sigma-alkylnickel intermediate that does not have beta-hydrogen atoms undergoes the insertion of a second alkene unit to cause a domino effect via a three-fold C-C bond formation process with and without the cleavage of one C-C bond.