铂催化3-炔-1-醇分子内加氢烷氧基化反应的理论研究  

Theoretical study on platinum-catalyzed intramolecular hydroalkoxylation of 3-alkyn-1-ol

作　　者：张兴辉 ZHANG Xing-Hui(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4期36-40,共5页Journal of Atomic and Molecular Physics

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

摘　　要：用密度泛函理论(DFT)M06-2X方法对铂催化的3-炔-1-醇分子内加氢烷氧基化反应机理和区域选择性进行了计算研究.计算结果表明:(1)通过羟基氧原子分别进攻分子内不同的炔烃碳原子形成两种竞争机制;(2)反应的关键步骤是分子内成环过程和氢迁移得到目标产物并释放催化剂的过程;(3)对于5-外切形成五元环产物的反应路径,具有相对较低的活化自由能;(4)两个竞争通道有一定的能量差,表明反应具有选择性但也会有副产物.计算研究结果与实验合成一致,并对实验报道给予了很好的补充和解释.The mechanism and regioselectivity of platinum-catalyzed intramolecular hydroalkoxylation of 3-alkyn-1-ol were calculated by the method of density functional theory(DFT)M06-2X.The calculation results show that:(1)Two competitive mechanisms are formed by attacking different alkyne carbon atoms in the molecule by hydroxyl oxygen atom;(2)The key step of the reaction is the process of intramolecular ring formation and hydrogen migration to obtain the target product and release the catalyst;(3)For the reaction path of 5-exo five-membered ring product,it has a relatively low activation free energy;(4)There is a certain energy difference between the two competing channels,indicating that the reaction is selective but there are also by-products.The calculation research results are consistent with the experimental synthesis,and give a good supplement and explanation to the experimental report.

关 键 词：铂催化 3-炔-1-醇 加氢烷氧基化 密度泛函理论 

分 类 号：O65[理学—分析化学]