Carbene-enabled ether activation through the formation of oxonium: a theoretical view

作     者：Ya-Nan Wang Xinghua Wang Shi-Jun Li Yu Lan 

作者机构：College of Chemistryand Institute of Green CatalysisZhengzhou University100 Science AvenueZhengzhou 450001HenanP.R.China School of Chemistry and Chemical Engineeringand Chongqing Key Laboratory of Theoretical and Computational ChemistryChongqing UniversityChongqing 400030P.R.China 

出 版 物：《Organic Chemistry Frontiers》 (有机化学前沿（英文）)

年 卷 期：2022年第9卷第5期

页      面：1247-1253页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：This project was supported by the National Natural Science Foundation of China(Grants 21903071,21822303 and 21772020) the Program for Science Technology Innovation Talents in Universities of Henan Province(No.20HASTIT004) 

主　　题：activation absolutely carbene 

摘      要：Here,we report a theoretical investigation of the reactivity and chemoselectivity of carbene-enabled ether *** mechanism obtained from DFT calculations revealed that the final products were dependent on the stability of the oxonium intermediate,which was afforded by nucleophilic attack of the corresponding ether onto a carbene ***,we found that the nucleophilicity of ethers was crucial but not their *** decomposition analysis based on absolutely localized molecular orbitals showed that the nucleophilicity of ethers was critical for polarization and charge transfer,leading to the chemoselectivity.