有机化学 ›› 2020, Vol. 40 ›› Issue (10): 3446-3451.DOI: 10.6023/cjoc202004015 上一篇    下一篇

研究论文

氰基硼氢化钠还原喹啉合成1,2-二氢喹啉

徐徐清风a, 黄显韵b, 张霄a, 游书力a,b   

  1. a 中国科学院上海有机化学研究所 金属有机化学国家重点实验室 上海 200032;
    b 华东理工大学药学院 上海 200237
  • 收稿日期:2020-04-10 修回日期:2020-05-09 发布日期:2020-05-15
  • 通讯作者: 游书力 E-mail:slyou@sioc.ac.cn
  • 基金资助:
    国家科技计划(No.2016YFA0202900)和国家自然科学基金(No.21821002)资助项目.

Synthesis of 1,2-Dihydroquinolines by Reduction of Quinolines with Sodium Cyanoborohydride

Xu-Xu Qing-Fenga, Huang Xian-Yunb, Zhang Xiaoa, You Shu-Lia,b   

  1. a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
    b School of Pharmacy, East China University of Science and Technology, Shanghai 200237
  • Received:2020-04-10 Revised:2020-05-09 Published:2020-05-15
  • Supported by:
    Project supported by the Ministry of Science and Technology of China (No. 2016YFA0202900) and the National Natural Science Foundation of China (No. 21821002).

1,2-二氢喹啉是一类重要的化合物.通过对已有方法的改进,发展了一类从喹啉出发高效合成1,2-二氢喹啉的反应(产率50%~96%).通过对一系列还原剂的筛选发现,当使用氰基硼氢化钠作为还原剂时,能有效克服已有方法中低转化率的问题,实现被活化的喹啉盐经还原去芳构化反应得到一系列N-烷氧羰基取代的1,2-二氢喹啉.需要指出的是,除3-位或4-位含有取代基的底物能得到单一的目标产物外,其他底物都会生成过度还原的四氢喹啉副产物,二氢喹啉与四氢喹啉比例均大于4:1.同时,该方法相较于文献中的方法操作简便,无须使用大大过量的氯甲酸酯,增强了反应的实用性.

关键词: 喹啉, 1,2-二氢喹啉, 去芳构化, 氰基硼氢化钠

An efficient conversion of quinolines to 1,2-dihydroquinolines (50%~96% yield) was developed via the modification of the known methods. It was found that using sodium cyanoborohydride as a reductant would overcome the low conversion often encountered in previous studies. A series of N-alkoxycarbonyl-1,2-dihydroquinolines were obtained through reduction of activated quinolium salts. Notably, with the exception of the 3-and 4-substituted substrates, a mixture of 1,2-dihydro-quinolines and the over reduced tetrahydroquinolines was obtained with the ratio over 4:1. Besides, compared to the established methods, an easy operation without using large excess of chloroformate further enhances practicability of the methodology.

Key words: quinoline, 1,2-dihydroquinoline, dearomatization, sodium cyanoborohydride