化学学报 ›› 2009, Vol. 67 ›› Issue (8): 833-837. 上一篇    下一篇

研究论文

简单亚胺的高效烯丙基化反应研究

魏晓宁 柳凌艳 王 冰 常卫星 李 靖*

  

  1. (元素有机国家重点实验室 南开大学 天津 300071)

  • 投稿日期:2008-09-17 修回日期:2008-12-19 发布日期:2009-04-28
  • 通讯作者: 李靖

Allylation Reaction of Simple Imines by Organotin Reagents

Wei, Xiaoning Liu, Lingyan Wang, Bing Chang, Weixing Li, Jing*   

  1. (State Key Laboratory of Elemento-organic Chemistry, Institute of Elemento-organic Chemistry, Nankai University, Tianjin 300071)

  • Received:2008-09-17 Revised:2008-12-19 Published:2009-04-28
  • Contact: Li, Jing

首次实现了In(OTf)3催化下二丁基二烯丙基锡对活性较低的简单亚胺的高效烯丙基化加成. 烯丙基锡试剂和亚胺底物在10 mol%的In(OTf)3催化下, 无需添加其它辅助试剂, 二氯甲烷中室温搅拌10 h, 就可以得到收率为80%~99%的高烯丙基胺产物. 用四烯丙基锡替换该体系中的二丁基二烯丙基锡, 50 mol%用量即能得到很好的结果. 同时还对反应的机理进行了探讨.

关键词: In(OTf)3, 烯丙基化, 亚胺, 二丁基二烯丙基锡, 四烯丙基锡

A new and effective allylation protocol was developed for less reactive simple imines using diallyldibutyltin in the presence of a catalytic amount of In(OTf)3. Allyltin reagents were reacted with imines in dichloromethane under 10 mol% In(OTf)3 without any other additives, to form homoallylic amines in moderate to good yields (80%~90%). In addition, a series of aldimines could be reacted with tetraallyltin in a 2∶1 molar ratio catalyzed by In(OTf)3 (10 mol%) to afford the corresponding products in good yields. A probable mechanistic pathway to explain the allylation process was depicted.

Key words: In(OTf)3, allylation, imine, diallyldibutyltin, tetraallyltin