有机化学 ›› 2017, Vol. 37 ›› Issue (10): 2663-2668.DOI: 10.6023/cjoc201704007 上一篇    下一篇

研究论文

通过铜催化氧化芳构化合成1,1'-联异喹啉

吕霞, 孟天卓, 郑波, 张义, 吴家家, 施小新   

  1. 华东理工大学药学院上海市化学生物学重点实验室 上海 200237
  • 收稿日期:2017-04-08 修回日期:2017-06-17 发布日期:2017-07-04
  • 通讯作者: 施小新 E-mail:xxshi@ecust.edu.cn
  • 基金资助:

    国家自然科学基金(No.20972048)资助项目.

Synthesis of 1,1'-Biisoquinolines via Cu-Catalyzed Oxidative Aromatization

Lü Xia, Meng Tianzhuo, Zheng Bo, Zhang Yi, Wu Jiajia, Shi Xiaoxin   

  1. Shanghai Key Laboratory of Chemical Biology, School of Pharmacy, East China University of Science and Technology, Shanghai 200237
  • Received:2017-04-08 Revised:2017-06-17 Published:2017-07-04
  • Contact: 10.6023/cjoc201704007 E-mail:xxshi@ecust.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No.20972048).

报道了一种合成1,1'-联异喹啉的实用新方法.N,N'-二苯乙基草酰胺(1a~1j)与三氯氧磷在氮气保护下于乙腈或甲苯中回流,发生Bischler-Napieralski环化反应生成3,3',4,4'-四氢-1,1'-联异喹啉(2a~2j).然后在二甲基亚砜(DMSO)溶剂中,以催化量的1,8-二氮杂双环[5,4,0]十一烯-7(DBU)为碱,化合物2a~2j在Cu(OAc)2催化下与空气发生氧化芳构化反应,生成一系列1,1'-联异喹啉3a~3j,二步总收率为70%~88%.

关键词: 1,1'-联异喹啉, Bischler-Napieralski环化, 铜催化, 氧化, 芳构化

A new method for practical synthesis of 1,1'-biisoquinolines is described. Treatment of N,N'-diphenethyloxal-amides (1a~1j) with phosphoryl trichloride in acetonitrile or toluene under N2 at reflux produced 3,3',4,4'-tetrahydro-1,1'-biisoquinolines (2a~2j) via Bischler-Napieralski cyclization. Subsequently, compounds 2a~2j underwent Cu(OAc)2-catalyzed aerobic oxidative aromatization in dimethyl sulfoxide (DMSO) in the presence of a catalytic amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to afford a series of 1,1'-biisoquinolines (3a~3j) in 70%~88% overall yields (2 steps).

Key words: 1,1'-biisoquinolines, Bischler-Napieralski cyclization, copper catalysis, oxidation, aromatization