1-(1,1-dimethylethoxycarbonyl)-2-(hydroxymethyl)-5-methylpyrrole | 175689-34-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: 1-(1,1-dimethylethoxycarbonyl)-2-(hydroxymethyl)-5-methylpyrrole
• 英文别名: tert-butyl 2-(hydroxymethyl)-5-methyl-1H-pyrrole-1-carboxylate；Tert-butyl 2-(hydroxymethyl)-5-methylpyrrole-1-carboxylate
• CAS: 175689-34-6
• 化学式: C₁₁H₁₇NO₃
• 分子量: 211.261
• InChiKey: AXQYJBVQMIXOAE-UHFFFAOYSA-N

物化性质

• 沸点：
  326.0±34.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  51.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-(1,1-dimethylethoxycarbonyl)-2-(hydroxymethyl)-5-methylpyrrole 在 sodium tetrahydroborate 、 4-乙酰氨基苯磺酰叠氮 、 sodium acetate 、 三乙胺 、 三氯氧磷 作用下， 以 甲醇 、 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 15.0h， 生成 <1-(1,1-dimethylethoxycarbonyl)-5-methyl-2-pyrrolyl>methyl 2-diazo-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
• 作为产物：
  描述：

  5-甲基-1H-吡咯-2-甲醛 在 sodium tetrahydroborate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 25.0h， 生成 1-(1,1-dimethylethoxycarbonyl)-2-(hydroxymethyl)-5-methylpyrrole
  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

• Azanorbornadienes as Thiol-Reactive Cleavable Linkers
  作者：Lucrezia De Pascalis、Srinivas Tekkam、M.G. Finn

  DOI：10.1021/acs.orglett.0c01912

  日期：2020.8.21

  Azanorbornadienes (ZNDs), prepared from pyrroles, undergo Michael reaction with thiols followed by retro-Diels-Alder (rDA) cleavage to release the starting pyrrole and a thiomaleate. Somewhat less reactive in this regard than furan-derived oxanorbornadienes, ZNDs have an additional point of variability at the pyrrole nitrogen center. Sulfonylated ZNDs were far more stable toward rDA cleavage than acylated analogues. tert-Butoxycarbonyl examples were much less reactive with thiols, rendering the rDA step slower than the initial conjugate addition.
• 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.