ethyl 2-cyano-3-(2-furyl)-5-oxohexanoate

• 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: ethyl 2-cyano-3-(2-furyl)-5-oxohexanoate
• 英文别名: Ethyl 2-cyano-3-(furan-2-yl)-5-oxohexanoate
• 化学式: C₁₃H₁₅NO₄
• 分子量: 249.266
• InChiKey: DTRFQAJPAXFRBX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  80.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  ethyl (E)-2-cyano-3-(2-furyl)-2-propenoate 、 乙酰乙酸烯丙酯 在 四(三苯基膦)钯 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以19%的产率得到ethyl 2-cyano-3-(2-furyl)-5-oxohexanoate
  参考文献：
  名称：

  Palladium Catalyzed Regioselective β-Acetonation−α-Allylation of Activated Olefins in One Shot

  摘要：

  The reaction of certain activated olefins 4 with allyl acetoacetate 5 in the presence of catalytic amounts of Pd(PPh3)(4) (5 mol %) in THF at room temperature gave the corresponding beta-acetonated alpha-allylated double addition products 6 regioselectively in good to excellent yields. The nature of the electron-withdrawing group in activated olefins affected significantly the reactivity of substrates; at least one of two electron-withdrawing groups of 4 should be a CN group. A proposed mechanism for this unprecedented three-component coupling reaction involves oxa-pi-allyl-pi-allylpalladium intermediate 3a (or its synthetic equivalents 3b-d). The in situ generation of activated olefins 4, from the aldehyde 11 and malononitrile 12, followed by the palladium-catalyzed reaction with allyl acetoacetate 5 also worked well, producing the corresponding three-component coupling products in good yields. Furthermore, allyltributylstannane 13 and alpha-chloro acetone 14 could be used as the alpha-allylation and beta-acetonation components, respectively, instead of allyl acetoacetate 5. The scope and limitations of palladium-catalyzed regioselective beta-acetonation-alpha-allylation reaction of activated olefins are described.

  DOI：

  10.1021/jo981719g

文献信息

• Palladium Catalyzed Regioselective β-Acetonation−α-Allylation of Activated Olefins in One Shot
  作者：Jae-Goo Shim、Hiroyuki Nakamura、Yoshinori Yamamoto

  DOI：10.1021/jo981719g

  日期：1998.11.1

  The reaction of certain activated olefins 4 with allyl acetoacetate 5 in the presence of catalytic amounts of Pd(PPh3)(4) (5 mol %) in THF at room temperature gave the corresponding beta-acetonated alpha-allylated double addition products 6 regioselectively in good to excellent yields. The nature of the electron-withdrawing group in activated olefins affected significantly the reactivity of substrates; at least one of two electron-withdrawing groups of 4 should be a CN group. A proposed mechanism for this unprecedented three-component coupling reaction involves oxa-pi-allyl-pi-allylpalladium intermediate 3a (or its synthetic equivalents 3b-d). The in situ generation of activated olefins 4, from the aldehyde 11 and malononitrile 12, followed by the palladium-catalyzed reaction with allyl acetoacetate 5 also worked well, producing the corresponding three-component coupling products in good yields. Furthermore, allyltributylstannane 13 and alpha-chloro acetone 14 could be used as the alpha-allylation and beta-acetonation components, respectively, instead of allyl acetoacetate 5. The scope and limitations of palladium-catalyzed regioselective beta-acetonation-alpha-allylation reaction of activated olefins are described.