(Z)-6H-5<3-ethylidene>-3-vinylpyran-2(5H)-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (Z)-6H-5<3-ethylidene>-3-vinylpyran-2(5H)-one
• 英文别名: tert-butyl (NE)-N-[(2E)-2-(5-ethenyl-6-oxopyran-3-ylidene)ethylidene]carbamate
• 化学式: C₁₄H₁₇NO₄
• 分子量: 263.293
• InChiKey: AQWWXQMAHHKXGG-NNGXMHFZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  65
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  吡咯-3-甲醛 在 sodium tetrahydroborate 、 辛酸铑 、 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 、 正己烷 、 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 41.0h， 生成 (Z)-6H-5<3-ethylidene>-3-vinylpyran-2(5H)-one
  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.