4,4-dimethyl-3-oxo-2-(1H-pyrrol-2-ylmethylidene)pentanenitrile

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 4,4-dimethyl-3-oxo-2-(1H-pyrrol-2-ylmethylidene)pentanenitrile
• 化学式: C₁₂H₁₄N₂O
• 分子量: 202.256
• InChiKey: UEOOMCUAQXOBBE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  56.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  benzyl 2-(acetoxymethyl)buta-2,3-dienoate 、 4,4-dimethyl-3-oxo-2-(1H-pyrrol-2-ylmethylidene)pentanenitrile 在 sodium carbonate 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 12.08h， 以93%的产率得到
  参考文献：
  名称：

  Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine

  摘要：

  Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of beta'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the beta'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, beta'C of allenoate 1 is an electrophilic center, and its beta'C and gamma C serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a gamma-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of gamma C and 1,3-dipole chemical behavior of beta C and beta'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.

  DOI：

  10.1021/jacs.5b03273
• 作为产物：
  描述：

  2-吡咯甲醛 、 新戊酰基乙腈 在 哌嗪 作用下， 以 乙醇 为溶剂， 生成 4,4-dimethyl-3-oxo-2-(1H-pyrrol-2-ylmethylidene)pentanenitrile
  参考文献：
  名称：

  Phosphine-Catalyzed Addition/Cycloaddition Domino Reactions of β′-Acetoxy Allenoate: Highly Stereoselective Access to 2-Oxabicyclo[3.3.1]nonane and Cyclopenta[a]pyrrolizine

  摘要：

  Two classes of phosphine-catalyzed addition/cycloaddition domino reactions of beta'-acetoxy allenoate 1 have been developed. The reaction of 1 with 2-acyl-3-methyl-acrylonitrile 2 readily occurs to give 2-oxabicyclo[3.3.1]nonane 3, furnishing the beta'-addition/[4 + 4] cycloaddition domino sequence. In this sequence, beta'C of allenoate 1 is an electrophilic center, and its beta'C and gamma C serve as a 1,4-dipole. When the other reaction partner is switched to 2-acyl-3-(2-pyrrole)-acrylonitrile 8, a gamma-addition/[3 + 2] cycloaddition domino reaction is instead observed, in which allenoate 1 exhibits dual electrophilic reactivity of gamma C and 1,3-dipole chemical behavior of beta C and beta'C. Furthermore, both of these two asymmetric variants have also been achieved with up to 93% ee. The domino reactions presented in this report are valuable for highly stereoselective construction of complex structures under mild reaction conditions.

  DOI：

  10.1021/jacs.5b03273

文献信息

• Construction of polycyclic frameworks via a DMAP-catalysed tandem addition–(4 + 2) annulation sequence of δ-acetoxy allenoate
  作者：Chunjie Ni、Yuejie Yuan、Yuwen Zhang、Jiangfei Chen、Dong Wang、Xiaofeng Tong

  DOI：10.1039/c7ob00688h

  日期：——

  Here is reported the DMAP-catalyzed addition/(4+2) annulation domino reaction of [small delta]-acetoxy allenoate with either salicylaldehyde-derived oxadiene or pyrrolealdehyde-derived oxadiene, which provides a facile method toward polycyclic frameworks. A cationic intermediate,...

  此处报道了小δ-乙酰氧基烯丙基酯与水杨醛衍生的恶二烯或吡咯醛衍生的恶二烯的DMAP催化的加成/（4 + 2）环化多米诺反应，其为多环骨架提供了一种简便的方法。阳离子中间体，...