银催化炔烃立体选择性氢烷基化反应的计算研究：泡利排斥作用控制/选择性
Computational study of silver-catalyzed stereoselective hydroalkylation of alkynes: Pauli repulsion controlled / selectivity.
作者信息
Hu Lingfei, Gao Han, Hu Yanlei, Lv Xiangying, Wu Yan-Bo, Lu Gang
机构信息
School of Chemistry and Chemical Engineering, Key Laboratory of Colloid and Interface Chemistry, Ministry of Education, Shandong University, Jinan, Shandong 250100, China.
Key Lab for Materials of Energy Conversion and Storage of Shanxi Province and Key Lab of Chemical Biology and Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, China.
出版信息
Chem Commun (Camb). 2021 Jun 29;57(52):6412-6415. doi: 10.1039/d1cc01917a.
The mechanism and origin of stereoselectivity of silver-catalyzed hydroalkylation of alkynes were computationally investigated at the B3LYP-D3BJ/6-311+G(d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ level. The complex of alkynyl trialkylboronate with cationic silver is a key intermediate, which triggers the rate- and stereoselectivity-determining 1,2-migration step. Energy decomposition analysis indicates that the difference of Pauli repulsion dominates the stereoselectivity.
在B3LYP-D3BJ/6-311+G(d,p)-SDD//B3LYP/6-31G(d)-LANL2DZ水平上，通过计算研究了银催化炔烃氢烷基化反应立体选择性的机理和起源。炔基三烷基硼酸酯与阳离子银的络合物是关键中间体，它引发了决定反应速率和立体选择性的1,2-迁移步骤。能量分解分析表明，泡利排斥作用的差异主导了立体选择性。
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