N-(1,3-dioxo-2-diazobutyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxaldehyde-O-methyloxime | 245051-75-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: N-(1,3-dioxo-2-diazobutyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxaldehyde-O-methyloxime
• 英文别名: 3-diazonio-4-[3-(methoxyiminomethyl)-3,4-dihydro-1H-isoquinolin-2-yl]-4-oxobut-2-en-2-olate
• CAS: 245051-75-6
• 化学式: C₁₅H₁₆N₄O₃
• 分子量: 300.317
• InChiKey: ZMBRYVBZAJHTTQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.83
• 重原子数：
  22.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  95.37
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  N-(1,3-dioxo-2-diazobutyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxaldehyde-O-methyloxime 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以87%的产率得到8a-acetyl-1-methoxy-1,1a,1b,2,7,8a-hexahydro-1,7a-diaza-cyclopropa[3,4]cyclopenta[1,2-b]naphthalen-8-one
  参考文献：
  名称：

  Intramolecular Aziridination:  Decomposition of Diazoamides with Tethered Imino Bonds

  摘要：

  Of three possible mechanistic pathways, tethered oximino ethers react intramolecularly with diazoamides to produce a diazabicyclo[5.1.0]hexane aziridine containing skeleton. Several acyclic and cyclic templates were synthesized and reacted with rhodium catalysts to prepare their corresponding annulated aziridines. Anomalous behavior was discovered with the piperidine template, resulting in an aziridination occurring during the attempted diazo-transfer reaction, rather than the catalyzed carbenoid reaction.

  DOI：

  10.1021/ol990750h
• 作为产物：
  描述：

  1,2,3,4-四氢-3-异喹啉羧酸 盐酸盐 在 吡啶 、 sodium hydroxide 、 硼烷四氢呋喃络合物 、 草酰氯 、 4-乙酰氨基苯磺酰叠氮 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 乙腈 、 叔丁醇 为溶剂， 反应 25.83h， 生成 N-(1,3-dioxo-2-diazobutyl)-1,2,3,4-tetrahydroisoquinoline-3-carboxaldehyde-O-methyloxime
  参考文献：
  名称：

  Intramolecular Aziridination:  Decomposition of Diazoamides with Tethered Imino Bonds

  摘要：

  Of three possible mechanistic pathways, tethered oximino ethers react intramolecularly with diazoamides to produce a diazabicyclo[5.1.0]hexane aziridine containing skeleton. Several acyclic and cyclic templates were synthesized and reacted with rhodium catalysts to prepare their corresponding annulated aziridines. Anomalous behavior was discovered with the piperidine template, resulting in an aziridination occurring during the attempted diazo-transfer reaction, rather than the catalyzed carbenoid reaction.

  DOI：

  10.1021/ol990750h

文献信息

• Facile generation of aziridines from the reaction of α-diazoamides with tethered oximino-ethers
  作者：Mark C. McMills、Dennis L. Wright、Jeffrey D. Zubkowski、Edward J. Valente

  DOI：10.1016/0040-4039(96)01567-5

  日期：1996.9

  In an attempt to prepare azomethine ylide intermediates for cycloaddition reactions with electron deficient olefins, oximino-ethers with tethered α-diazoamide moieties were reacted in the presence of metal catalyst. The reaction resulted in aziridine formation preferentially.

  为了制备用于与缺电子烯烃的环加成反应的偶氮甲碱叶立德中间体，在金属催化剂的存在下，使具有系链的α-重氮酰胺基团的肟基醚反应。该反应优先导致形成氮丙啶。