有机化学 ›› 2019, Vol. 39 ›› Issue (8): 2157-2165.DOI: 10.6023/cjoc201906005 上一篇    下一篇

所属专题: 元素有机化学合辑2018-2019 陈茹玉先生诞辰100周年

研究论文

叔膦介导的叠氮化合物与不饱和酮的连续Staudinger/Aza-Michael加成反应合成β-氨基取代酮类化合物

丛甜甜a, 王华敏a, 刘媛媛a, 吴海虹a, 张俊良a,b   

  1. a 华东师范大学化学与分子工程学院 上海市绿色化学与化工过程绿色化重点实验室 上海 200062;
    b 复旦大学化学系 上海 200438
  • 收稿日期:2019-06-06 修回日期:2019-07-09 发布日期:2019-07-17
  • 通讯作者: 刘媛媛, 吴海虹, 张俊良 E-mail:yyliu@chem.ecnu.edu.cn;hhwu@chem.ecnu.edu.cn;junliangzhang@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(No.21871088)、上海市教育发展基金会和上海市教育委员会“晨光计划”(No.16CG22)、中央高校基本科研业务费专项资金(No.21871088)资助项目.

Phosphine-Mediated Sequential Staudinger/Aza-Michael Addition of Azides with Unsaturated Ketones to Synthesize β-Amino Substituted Ketones

Cong Tiantiana, Wang Huamina, Liu Yuanyuana, Wu Haihonga, Zhang Junlianga,b   

  1. a Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062;
    b Department of Chemistry, Fudan University, Shanghai 200438
  • Received:2019-06-06 Revised:2019-07-09 Published:2019-07-17
  • Contact: 10.6023/cjoc201906005 E-mail:yyliu@chem.ecnu.edu.cn;hhwu@chem.ecnu.edu.cn;junliangzhang@fudan.edu.cn
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21871088), the Chenguang Program supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission (No. 16CG22), and the Fundamental Research Funds for the Central Universities (No. 21871088).

以叔膦为介导,水为添加剂,在1,2-二氯乙烷溶剂中,叠氮化合物与三氟甲基取代αβ-不饱和酮为原料,发生连续Staudinger/Aza-Michael加成反应.所开发反应可以中等到优秀的收率(最高96%)获得氢胺化产物,并且能够实现克级规模制备目标产物.此方法有广泛的底物范围(30个底物).核磁共振磷谱监测实验验证了反应的启动步骤是叠氮与叔膦的Staudinger反应.

关键词: 叔膦, Staudinger反应, 氮杂Michael加成, 叠氮, 氢胺化, 烯烃

A phosphine-mediated Staudinger/Aza-Michael addition of azides with trifluoromethyl substituted α,β-unsaturated ketones was developed, giving hydroamination products in medium to good yields (up to 96%). The hydroamination products could be prepared on gram scale and a wide range of substrates are tolerated under the optimized reaction conditions (30 examples). 31P NMR experiments indicate that this reaction was initiated by Staudinger reaction of azide with phosphine.

Key words: phosphines, Staudinger reaction, aza-Michael addition, azides, hydroamination, alkenes