2-trimethylsilylethyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxy-3-methylpiperidine-1-carboxylate | 243865-40-9

• 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: 2-trimethylsilylethyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxy-3-methylpiperidine-1-carboxylate
• CAS: 243865-40-9
• 化学式: C₁₉H₃₅NO₃Si
• 分子量: 353.577
• InChiKey: OERHQGHNQYIBOA-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.79
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-trimethylsilylethyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxy-3-methylpiperidine-1-carboxylate 在 四丁基氟化铵 、 lithium perchlorate 、 三氟乙酸 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 86.0h， 生成 (7aα,9aβ,9bβ)-5,9a-dimethyl-2,3,5,7a,8,9,9a,9b-octahydro-1H-cyclopenta[ij]quinolizine
  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：

  3-(hepta-4(E),6-dienyl)-3-methyl-2-oxopiperidine-1-carboxylic acid [2-(trimethylsilyl)ethyl] ester 在 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 以98%的产率得到2-trimethylsilylethyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxy-3-methylpiperidine-1-carboxylate
  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