tert-butyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxypiperidine-1-carboxylate | 243865-34-1

• 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: tert-butyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxypiperidine-1-carboxylate
• CAS: 243865-34-1
• 化学式: C₁₇H₂₉NO₃
• 分子量: 295.422
• InChiKey: RFTSCAXNYGAQCN-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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：

  tert-butyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxypiperidine-1-carboxylate 在 camphor-10-sulfonic acid 、 lithium perchlorate 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 2.0h， 以52%的产率得到(1α,6aβ,9aα,9bβ)-1-vinyl-4,5,6,6a,7,8,9,9a-octahydro-2-oxa-3a-aza-phenalen-3-one
  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)-2-piperidone 在 三乙基硼氢化锂 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 生成 tert-butyl 3-[(4E)-hepta-4,6-dienyl]-2-hydroxypiperidine-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

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.