<1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>methyl 3-oxopentanoate | 175689-43-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: <1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>methyl 3-oxopentanoate
• 英文别名: Tert-butyl 2-(3-oxopentanoyloxymethyl)pyrrole-1-carboxylate
• CAS: 175689-43-7
• 化学式: C₁₅H₂₁NO₅
• 分子量: 295.335
• InChiKey: MIIDEMRREYWCAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  21
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  74.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  <1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>methyl 3-oxopentanoate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 生成 <1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>methyl 2-diazo-3-<(1,1-dimethylethyl)dimethylsiloxy>-3-pentenoate
  参考文献：
  名称：

  Divergent Pathways in the Intramolecular Reactions between Rhodium-Stabilized Vinylcarbenoids and Pyrroles:  Construction of Fused Tropanes and 7-Azabicyclo[4.2.0]octadienes

  摘要：

  The rhodium(II)-catalyzed intramolecular reaction between vinyldiazomethanes and pyrroles leads to a novel synthesis of fused tropanes. The reaction occurs by a stepwise 3 + 4 annulation mechanism between a rhodium-stabilized vinylcarbenoid intermediate and the pyrrole rather than by the typical tandem cyclopropanation/Cope rearrangement sequence. The outcome of the reaction is very sensitive to the vinylcarbenoid structure. In particular, the presence of a 2-siloxy substituent on the vinylcarbenoid strongly favors the formation of fused tropanes. In the absence of such functionality, the formation of fused 7-azabicyclo[4.2.0]octadienes becomes the dominant reaction pathway.

  DOI：

  10.1021/jo952127q
• 作为产物：
  描述：

  2-醛基吡咯-1-甲酸叔丁酯 在 吡啶 、 sodium tetrahydroborate 作用下， 以 甲醇 、 苯 为溶剂， 反应 15.0h， 生成 <1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>methyl 3-oxopentanoate
  参考文献：
  名称：

  Divergent Pathways in the Intramolecular Reactions between Rhodium-Stabilized Vinylcarbenoids and Pyrroles:  Construction of Fused Tropanes and 7-Azabicyclo[4.2.0]octadienes

  摘要：

  The rhodium(II)-catalyzed intramolecular reaction between vinyldiazomethanes and pyrroles leads to a novel synthesis of fused tropanes. The reaction occurs by a stepwise 3 + 4 annulation mechanism between a rhodium-stabilized vinylcarbenoid intermediate and the pyrrole rather than by the typical tandem cyclopropanation/Cope rearrangement sequence. The outcome of the reaction is very sensitive to the vinylcarbenoid structure. In particular, the presence of a 2-siloxy substituent on the vinylcarbenoid strongly favors the formation of fused tropanes. In the absence of such functionality, the formation of fused 7-azabicyclo[4.2.0]octadienes becomes the dominant reaction pathway.

  DOI：

  10.1021/jo952127q

文献信息

• Divergent Pathways in the Intramolecular Reactions between Rhodium-Stabilized Vinylcarbenoids and Pyrroles:  Construction of Fused Tropanes and 7-Azabicyclo[4.2.0]octadienes
  作者：Huw M. L. Davies、Julius J. Matasi、Gulzar Ahmed

  DOI：10.1021/jo952127q

  日期：1996.1.1

  The rhodium(II)-catalyzed intramolecular reaction between vinyldiazomethanes and pyrroles leads to a novel synthesis of fused tropanes. The reaction occurs by a stepwise 3 + 4 annulation mechanism between a rhodium-stabilized vinylcarbenoid intermediate and the pyrrole rather than by the typical tandem cyclopropanation/Cope rearrangement sequence. The outcome of the reaction is very sensitive to the vinylcarbenoid structure. In particular, the presence of a 2-siloxy substituent on the vinylcarbenoid strongly favors the formation of fused tropanes. In the absence of such functionality, the formation of fused 7-azabicyclo[4.2.0]octadienes becomes the dominant reaction pathway.