3-(2-azidoethyl)-1-<3,4-(methylenedioxy)phenyl>cyclohex-1-ene | 144344-97-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并间二氧杂环戊烯类
• 英文名称: 3-(2-azidoethyl)-1-<3,4-(methylenedioxy)phenyl>cyclohex-1-ene
• 英文别名: 1-<3,4-(Methylenedioxy)phenyl>-3-(2-azidoethyl)cyclohex-1-ene；1,3-Benzodioxole, 5-[3-(2-azidoethyl)-1-cyclohexen-1-yl]-；5-[3-(2-azidoethyl)cyclohexen-1-yl]-1,3-benzodioxole
• CAS: 144344-97-8
• 化学式: C₁₅H₁₇N₃O₂
• 分子量: 271.319
• InChiKey: UOZYPWQXHBFVPC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  32.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(2-azidoethyl)-1-<3,4-(methylenedioxy)phenyl>cyclohex-1-ene 在 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 30.0h， 生成 (3aR*,7S*,7aS*)-7-<3,4-(methylenedioxy)phenyl>-2,3,3a,4,5,6,7,7a,-octahydroindole
  参考文献：
  名称：

  Synthesis of (.+-.)-.gamma.-lycorane by the intramolecular cycloaddition of an azide with an .omega.-chloroalkene

  摘要：

  Cyclization of 1-[2-(chloromethyl)-4,5-(methylenedioxy)phenyl]-3-(2-azidoethyl)cyclohex-1-ene (16) in benzene at 140-degrees-C caused the following sequence of events: (1) intramolecular 1,3-dipolar cycloaddition of the azide onto the alkene: (2) formation of an imine by loss of nitrogen from the triazoline intermediate with concomitant hydrogen migration:and (3) intramolecular N-alkylation of the imine nitrogen with the benzylic chloride. Without isolation, the resultant iminium ion was reduced with sodium borohydride to give (+/-)-gamma-lycorane (3). The cyclization precursor 16 was prepared a novel allylic substitution reaction, where the allylic alcohol 10 or the allylic acetate 11 was treated with 1-ethoxy-1-[(tert-butyldimethylsilyl)oxy]ethene and lithium perchlorate in ether to produce the gamma,delta-unsaturated ester 12. An alternative synthesis of (+/-)-gamma-lycorane (3) was accomplished using a similar 1,3-dipolar cycloaddition approach, except that the benzylic chloride functionality was absent (i.e., 26 --> 27). Reduction of the resultant imine followed by a Bischler-Napieralski cyclization gave the known lactam 31, which had previously been converted to (+/-)-gamma-lycorane.

  DOI：

  10.1021/jo00051a021
• 作为产物：
  描述：

  3,4-methylenedioxyphenyllithium 在 lithium aluminium tetrahydride 、 n-Bu₄N₃ 、 lithium perchlorate 、 三乙胺 作用下， 生成 3-(2-azidoethyl)-1-<3,4-(methylenedioxy)phenyl>cyclohex-1-ene
  参考文献：
  名称：

  烷基叠氮化物与碳阳离子的分子内施密特反应。构象受限的仲氨基重氮离子的产生和重排。

  摘要：

  azidoalkene的治疗2与三氟甲磺酸制备的桥连双环烯胺3通过分子内施密特反应。中间氨基重氮离子5的重排是完全区域选择性的。

  DOI：

  10.1016/s0040-4039(00)79075-7

文献信息

• Intramolecular Schmidt reactions of azides with carbocations: synthesis of bridged-bicyclic and fused-bicyclic tertiary amines
  作者：William H. Pearson、Rajesh Walavalkar、Jeffrey M. Schkeryantz、Wen Kui Fang、James D. Blickensdorf

  DOI：10.1021/ja00075a038

  日期：1993.11

  Aliphatic azides were captured intramolecularlyby carbocations, producing aminodiazonium ion intermediates. Carbon-to-nitrogen rearrangement then occurred, generating bridged- or fused-bicyclic a-amino carbocations or iminium ions, depending on the geometry about the C(+)-N bond. In the bridged systems, rapid elimination of the α-amino carbocations produced twisted enamines with 1-azabicyclo[3.2.2]nonene

  脂肪族叠氮化物被碳正离子分子内捕获，产生氨基重氮离子中间体。然后发生碳氮重排，产生桥连或稠合双环 a-氨基碳正离子或亚胺离子，具体取决于 C(+)-N 键的几何形状。在桥接系统中，α-氨基碳阳离子的快速消除产生具有 1-氮杂双环 [3.2.2] 壬烯、1-氮杂双环 [2.2.2] 辛烯和 1-氮杂双环 [3.2.1] 辛烯骨架的扭曲烯胺。在稠合系统中，亚胺离子被硼氢化钠还原为 1-氮杂双环 [n.3.0] 烷烃，其中 n=4 或 5。这些分子内施密特反应的碳正离子是通过用三氟甲磺酸处理烯烃或醇而产生的