有机化学 ›› 2022, Vol. 42 ›› Issue (8): 2456-2461.DOI: 10.6023/cjoc202202022 上一篇    下一篇

研究论文

邻甲酰基苯甲酸甲酯还原胺化/内酰胺化一锅法合成N-取代异吲哚-1-酮

张文生a,*(), 李焱b, 崔海燕a, 苏小莉a, 徐素鹏a   

  1. a 济源职业技术学院冶金化工系 河南济源 459000
    b 焦作师范高等专科学校合成技术研究所 河南焦作 454100
  • 收稿日期:2022-02-19 修回日期:2022-04-08 发布日期:2022-05-17
  • 通讯作者: 张文生
  • 基金资助:
    河南省科技攻关计划(212102310883); 河南省教育厅自然科学重点研究(21B150013); 济源职业技术学院自然科学重点研究(JZXY-2020-58)

One-Pot Synthesis of N-Substituted Isoindolin-1-ones via Reductive Amination/Lactamization of Methyl 2-Formylbenzoate

Wensheng Zhanga(), Yan Lib, Haiyan Cuia, Xiaoli Sua, Supeng Xua   

  1. a Department of Metallurgy and Chemical Engineering, Jiyuan Vocational and Technical College, Jiyuan, Henan 459000
    b Institute of Synthetic Technology, Jiaozuo Normal College, Jiaozuo, Henan 454100
  • Received:2022-02-19 Revised:2022-04-08 Published:2022-05-17
  • Contact: Wensheng Zhang
  • Supported by:
    Program for Science and Technology Development of Henan Province(212102310883); Key Natural Science Research Program of the Education Department of Henan Province(21B150013); Key Natural Scientific Research Projects of Jiyuan Vocational Technical College(JZXY-2020-58)

报道了一种通过邻醛基苯甲酸甲酯的胺化还原/内酰胺化一锅法合成N-取代异吲哚-1-酮的高效方法. 反应包括以NaBH3CN为还原剂, 邻醛基苯甲酸甲酯与伯芳基胺或烷基胺的胺化还原以及N原子对羰基碳的分子内亲核进攻过程. 对于4-取代芳胺、烷基胺和邻甲基苯胺, 该反应可以在室温下的二氯乙烷中顺利完成转化. 而其他的2-取代芳胺, 则需K2CO3 (2 equiv.)促进下在乙腈中回流8 h完成. 该反应的底物适用范围很广, 最高收率可达99%.

关键词: N-取代异吲哚-1-酮, 胺化还原, 内酰胺化, 一锅法合成

An efficient, one-pot synthesis of N-substituted isoindolin-1-ones by an aminative reduction/lactamisation sequence of methyl 2-formylbenzoate is introduced. The reaction process includes aminative reduction of o-phthalaldehydic acid methylesters with primary aryl or alkyl amines using NaBH3CN and the following intramolecular nucleophilic N-attack on carbonyl carbon atom. For 4-substituted aromatic amines, alkyl amines and o-methylaniline, the transformation can be successfully completed in 1,2-dichloroethane at room temperature. For other 2-substituted aromatic amines, reflux in acetonitrile for 8 h in the presence of K2CO3 (2 equiv.) is needed. The reaction scopes were quite broad and up to 96% yield of diverse products was achieved.

Key words: N-substituted isoindolin-1-ones, aminative reduction, lactamisation, one-pot synthesis