铜介导的三甲基硅基叠氮化物一锅还原胺化芳基卤化物的机理研究。

Mechanism study of copper-mediated one-pot reductive amination of aryl halides using trimethylsilyl azide.

机构信息

Laboratory of Organic Chemistry, Gifu Pharmaceutical University , 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan.

出版信息

J Org Chem. 2013 Sep 20;78(18):8980-5. doi: 10.1021/jo401474k. Epub 2013 Aug 30.

Abstract

Reaction mechanisms of the copper-mediated amination of aryl halides with trimethylsilyl azide (TMSN3) were analyzed on the basis of the time-course study using reaction monitoring FT-IR, trapping an intermediary aryl azide by the Huisgen reaction, and the analysis of the generated N2 gas during the reaction. This amination would proceed through multiple pathways via aryl radicals and copper(I) azide.

摘要

基于使用反应监测傅里叶变换红外光谱、通过 Huisgen 反应捕获中间体芳基叠氮化物以及分析反应过程中生成的 N2 气体的时程研究，分析了三甲基硅基叠氮化物 (TMSN3) 与芳基卤化物的铜介导胺化反应的反应机制。该胺化反应可能通过芳基自由基和一价铜叠氮化物的多种途径进行。