铱催化叠氮化物和亚酰胺环加成反应的密度泛函研究  

Density functional study on the iridium-catalyzedcycloaddition reaction of azide-ynamide

作　　者：张兴辉 师海雄 姜立萍 牛腾 李姗姗 王子宜 ZHANG Xing-Hui;SHI Hai-Xiong;JIANG Li-Ping;NIU Teng;LI Shan-Shan;WANG Zi-Yi(College of Chemical Engineering,Lanzhou University of Arts and Science,Lanzhou 730010,China)

机构地区：[1]兰州文理学院化工学院,兰州730010

出　　处：《原子与分子物理学报》2021年第2期87-91,共5页Journal of Atomic and Molecular Physics

基　　金：甘肃省自然科学基金项目(20JR5RA479);兰州文理学院杰出青年研究计划项目(2018JCQN008)。

摘　　要：用密度泛函理论(DFT) B3LYP方法对铱催化的环加成合成5-氨基1,2,3-三唑化合物机理进行了计算研究.计算结果表明:(1)通过叠氮化合物的端基氮分别进攻不同炔烃碳原子形成两种竞争机制;(2)释放催化剂得到目标产物的还原消除过程是反应的关键步骤;(3)对于进攻苯基一侧炔烃碳原子的反应通道,具有相对较低的活化自由能;(4)两个竞争通道存在一定的能量差,表明反应具有较好的选择性,计算研究对实验报道进行了很好的补充和解释.The mechanism of the synthesis of 5-amino1,2,3-triazole by cycloaddition catalyzed by iridium was calculated by the B3 LYP method of density functional theory(DFT).The calculation results show that:(1) the terminal nitrogen of the azide compound attacks two different alkyne carbon atoms to form two competitive mechanisms;(2) the reduction and elimination process of the target product released by the catalyst is the key step of the reaction;The reaction channel attacking the alkyne carbon atom on the phenyl side has a relatively low activation free energy;(4) There is a certain energy difference between the two competing channels,indicating that the reaction has good selectivity.Computational research is a good supplement and explanation for the experimental reports.

关 键 词：密度泛函理论 铱催化 环加成反应 1 2 3-三唑 

分 类 号：O65[理学—分析化学]