2-<1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>ethyl 2-diazo-3-<(1,1-dimethylethyl)dimethylsiloxy>-3-butenoate | 175689-50-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 2-<1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>ethyl 2-diazo-3-<(1,1-dimethylethyl)dimethylsiloxy>-3-butenoate
• 英文别名: Tert-butyl 2-[2-[3-[tert-butyl(dimethyl)silyl]oxy-2-diazobut-3-enoyl]oxyethyl]pyrrole-1-carboxylate
• CAS: 175689-50-6
• 化学式: C₂₁H₃₃N₃O₅Si
• 分子量: 435.596
• InChiKey: FHGPDSAXIQIXTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  30
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-<1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>ethyl 2-diazo-3-<(1,1-dimethylethyl)dimethylsiloxy>-3-butenoate 在 rhodium(II) N-(p-(tert-butyl)phenylsulfonyl)-prolinate 作用下， 以 正己烷 为溶剂， 反应 1.0h， 以32%的产率得到1,1-dimethyl 3,4,7,8-tetrahydro-9-<(1,1-dimethylethyl)dimethylsiloxy>-1-oxo-1H-cycloheptapyran-4aα,7α-imine-10-carboxylate
  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-(1H-吡咯-2-基)乙醇 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 28.5h， 生成 2-<1-(1,1-dimethylethoxycarbonyl)-2-pyrrolyl>ethyl 2-diazo-3-<(1,1-dimethylethyl)dimethylsiloxy>-3-butenoate
  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