1-bromo-11,11-dimethyl-10-(2-methylallyl)-9-azatricyclo[6.2.2.0^2,7]dodeca-2,4,6-triene

• 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: 1-bromo-11,11-dimethyl-10-(2-methylallyl)-9-azatricyclo[6.2.2.0^2,7]dodeca-2,4,6-triene
• 英文别名: (1S,8S,10S)-1-bromo-11,11-dimethyl-10-(2-methylprop-2-enyl)-9-azatricyclo[6.2.2.02,7]dodeca-2,4,6-triene
• 化学式: C₁₇H₂₂BrN
• 分子量: 320.272
• InChiKey: VLAOEMUWJQPNBS-ZOBUZTSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  苦味酸 、 1-bromo-11,11-dimethyl-10-(2-methylallyl)-9-azatricyclo[6.2.2.0^2,7]dodeca-2,4,6-triene 以87%的产率得到
  参考文献：
  名称：

  摘要：

  Allylmetallation of isoquinolines, quinoline, and quinoxaline with allylic derivatives of zinc was examined for the first time. A convenient procedure was discovered and developed for the synthesis of 1,4-ethano-2,3-dihydroisoquinolines based on the reactions of isoquinolines with allylic derivatives of zinc. This multistage process involves double allylmetallation of the heterocyclic ring followed by cyclization through intramolecular carbometallation of the C=C bond. The structures of three key derivatives of 1,4-ethano-2,3-dihydroisoquinoline were established by X-ray diffraction analysis. The reactions of quinoxaline with allyl- and methallylzinc bromide proceeded stereospecifically to form trans-2,3-diallylated 1,2,3,4-tetrahydroquinoxalines. Heating of quinoline with methallylzinc bromide in THF afforded 4-methallylquinoline in nearly quantitative yield. The initially formed 1,4-metallation product underwent aromatization through elimination of HZnBr.

  DOI：

  10.1023/a:1015065721466
• 作为产物：
  描述：

  4-溴异喹啉 、 bromozinc(1+),2-methanidylprop-1-ene 在 sodium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 生成 1-bromo-11,11-dimethyl-10-(2-methylallyl)-9-azatricyclo[6.2.2.0^2,7]dodeca-2,4,6-triene
  参考文献：
  名称：

  摘要：

  Allylmetallation of isoquinolines, quinoline, and quinoxaline with allylic derivatives of zinc was examined for the first time. A convenient procedure was discovered and developed for the synthesis of 1,4-ethano-2,3-dihydroisoquinolines based on the reactions of isoquinolines with allylic derivatives of zinc. This multistage process involves double allylmetallation of the heterocyclic ring followed by cyclization through intramolecular carbometallation of the C=C bond. The structures of three key derivatives of 1,4-ethano-2,3-dihydroisoquinoline were established by X-ray diffraction analysis. The reactions of quinoxaline with allyl- and methallylzinc bromide proceeded stereospecifically to form trans-2,3-diallylated 1,2,3,4-tetrahydroquinoxalines. Heating of quinoline with methallylzinc bromide in THF afforded 4-methallylquinoline in nearly quantitative yield. The initially formed 1,4-metallation product underwent aromatization through elimination of HZnBr.

  DOI：

  10.1023/a:1015065721466

文献信息

• ——
  作者：Yu. N. Bubnov、F. V. Pastukhov、Z. A. Starikova、A. V. Ignatenko

  DOI：10.1023/a:1015065721466

  日期：——

  Allylmetallation of isoquinolines, quinoline, and quinoxaline with allylic derivatives of zinc was examined for the first time. A convenient procedure was discovered and developed for the synthesis of 1,4-ethano-2,3-dihydroisoquinolines based on the reactions of isoquinolines with allylic derivatives of zinc. This multistage process involves double allylmetallation of the heterocyclic ring followed by cyclization through intramolecular carbometallation of the C=C bond. The structures of three key derivatives of 1,4-ethano-2,3-dihydroisoquinoline were established by X-ray diffraction analysis. The reactions of quinoxaline with allyl- and methallylzinc bromide proceeded stereospecifically to form trans-2,3-diallylated 1,2,3,4-tetrahydroquinoxalines. Heating of quinoline with methallylzinc bromide in THF afforded 4-methallylquinoline in nearly quantitative yield. The initially formed 1,4-metallation product underwent aromatization through elimination of HZnBr.