3-(octa-4(E),6(E)-dienyl)-2-oxopiperidine-1-carboxylic acid [2-(trimethylsilyl)ethyl] ester | 243865-47-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-(octa-4(E),6(E)-dienyl)-2-oxopiperidine-1-carboxylic acid [2-(trimethylsilyl)ethyl] ester
• 英文别名: 2-trimethylsilylethyl 3-[(4E,6E)-octa-4,6-dienyl]-2-oxopiperidine-1-carboxylate
• CAS: 243865-47-6
• 化学式: C₁₉H₃₃NO₃Si
• 分子量: 351.561
• InChiKey: MUBPEXRXLIEFJA-BSWSSELBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.0
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(octa-4(E),6(E)-dienyl)-2-oxopiperidine-1-carboxylic acid [2-(trimethylsilyl)ethyl] ester 在 六甲基磷酰三胺 、 三乙基硼氢化锂 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 2-Hydroxy-3-methyl-3-((4E,6E)-octa-4,6-dienyl)-piperidine-1-carboxylic acid 2-trimethylsilanyl-ethyl ester
  参考文献：
  名称：

  Construction of Carbocyclic Arrays Containing Nitrogen via Intramolecular Imino Diels−Alder Reactions in Polar Media. A Comparative Study:  5.0 M Lithium Perchlorate−Diethyl Ether versus Water

  摘要：

  The intramolecular Diels-Alder reaction of iminium ions has been examined in polar media such as 5.0 M lithium perchlorate-diethyl ether and water. Cycloaddition of 3 in 5.0 M, lithium perchlorate-diethyl ether containing 10 mol % camphorsulfonic acid proceeds, not by in situ generation of iminium ion 1, but rather via N-(acyloxy)iminium ion 7 which subsequently cyclizes to tricyclic compounds 4 and 5. Direct formation of imines 15 and 30 was realized by reduction of the corresponding lactams (13 and 29, respectively) followed by exposure to 2.0 equiv of tetra-n-butylammonium fluoride. Exposure of the trifluoroacetic acid salt 18 of imine 15 to 5.0 M lithium perchlorate-diethyl ether at ambient temperature gave rise to tricyclic amine 16 in which the diene underwent isomerization prior to [4+2] cycloaddition. In contrast, use of water provided tricyclic amine 19. Similarly, exposure of iminium salt 31 to water afforded tricyclic amine 32. The polar sovent of choice for intramolecular imino Diels-Alder reactions employing substrates such as 18 and 31 is water.

  DOI：

  10.1021/jo9905930
• 作为产物：
  描述：

  (4E,6E)-octa-4,6-dien-1-ol 在 咪唑 、 正丁基锂 、 碘 、 三苯基膦 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 3-(octa-4(E),6(E)-dienyl)-2-oxopiperidine-1-carboxylic acid [2-(trimethylsilyl)ethyl] ester
  参考文献：
  名称：

  Construction of Carbocyclic Arrays Containing Nitrogen via Intramolecular Imino Diels−Alder Reactions in Polar Media. A Comparative Study:  5.0 M Lithium Perchlorate−Diethyl Ether versus Water

  摘要：

  The intramolecular Diels-Alder reaction of iminium ions has been examined in polar media such as 5.0 M lithium perchlorate-diethyl ether and water. Cycloaddition of 3 in 5.0 M, lithium perchlorate-diethyl ether containing 10 mol % camphorsulfonic acid proceeds, not by in situ generation of iminium ion 1, but rather via N-(acyloxy)iminium ion 7 which subsequently cyclizes to tricyclic compounds 4 and 5. Direct formation of imines 15 and 30 was realized by reduction of the corresponding lactams (13 and 29, respectively) followed by exposure to 2.0 equiv of tetra-n-butylammonium fluoride. Exposure of the trifluoroacetic acid salt 18 of imine 15 to 5.0 M lithium perchlorate-diethyl ether at ambient temperature gave rise to tricyclic amine 16 in which the diene underwent isomerization prior to [4+2] cycloaddition. In contrast, use of water provided tricyclic amine 19. Similarly, exposure of iminium salt 31 to water afforded tricyclic amine 32. The polar sovent of choice for intramolecular imino Diels-Alder reactions employing substrates such as 18 and 31 is water.

  DOI：

  10.1021/jo9905930

文献信息

• Construction of Carbocyclic Arrays Containing Nitrogen via Intramolecular Imino Diels−Alder Reactions in Polar Media. A Comparative Study:  5.0 M Lithium Perchlorate−Diethyl Ether versus Water
  作者：Paul A. Grieco、Michael D. Kaufman

  DOI：10.1021/jo9905930

  日期：1999.8.1

  The intramolecular Diels-Alder reaction of iminium ions has been examined in polar media such as 5.0 M lithium perchlorate-diethyl ether and water. Cycloaddition of 3 in 5.0 M, lithium perchlorate-diethyl ether containing 10 mol % camphorsulfonic acid proceeds, not by in situ generation of iminium ion 1, but rather via N-(acyloxy)iminium ion 7 which subsequently cyclizes to tricyclic compounds 4 and 5. Direct formation of imines 15 and 30 was realized by reduction of the corresponding lactams (13 and 29, respectively) followed by exposure to 2.0 equiv of tetra-n-butylammonium fluoride. Exposure of the trifluoroacetic acid salt 18 of imine 15 to 5.0 M lithium perchlorate-diethyl ether at ambient temperature gave rise to tricyclic amine 16 in which the diene underwent isomerization prior to [4+2] cycloaddition. In contrast, use of water provided tricyclic amine 19. Similarly, exposure of iminium salt 31 to water afforded tricyclic amine 32. The polar sovent of choice for intramolecular imino Diels-Alder reactions employing substrates such as 18 and 31 is water.