论文部分内容阅读
叠氮化合物和膦硫酯的无痕施陶丁格连接反应是一种有效生成酰胺键的方法.通过密度泛函方法研究了无痕施陶丁格连接的反应机理.计算结果表明反应的决速步为反应的第一步,即膦进攻叠氮的端基氮,形成膦基叠氮化物的过程.膦亚胺中间体形成之后,向不同方向转化(酰基迁移后水解或者直接水解)的难易程度决定了最终产物的组成.对几种不同偶联试剂介导的无痕施陶丁格连接反应的计算结果,都与实验数据相吻合.
The traceless Staudinger ligation reaction of azide and phosphine thioester is a promising method for the formation of amide bonds. The reaction mechanism of the non-staged Staudinger ligation was investigated by density functional method. The calculated results show that the reaction The fast step is the first step in the reaction, that is, the phosphine attacks the terminal nitrogen of the azide to form a phosphino azide. After the formation of the phosphinimine intermediate, it is converted in different directions (hydrolyzed or directly hydrolyzed by the acyl group) The degree of difficulty determines the composition of the final product.The calculation results of the non-stained Staudinger ligation reaction mediated by several different coupling reagents are consistent with the experimental data.