Electric-field-controlled highly regioselective thiocyanation of N-containing heterocycles  

作　　者：Ming Gong Qian Wu Jung Keun Kim Mengmeng Huang Yabo Li Yangjie Wu Jong Seung Kim 

机构地区：[1]Henan Key Laboratory of Chemical Biology and Organic Chemistry,Key Laboratory of Applied Chemistry of Henan Universities,College of Chemistry,Zhengzhou University,Zhengzhou 450052,China [2]Department of Chemistry,Korea University,Seoul 02841,Korea

出　　处：《Science China Chemistry》2024年第4期1263-1269,共7页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21172200,21302172);the Basic Research Training Project of Zhengzhou University(JC2020053021);supported by the National Research Foundation of Korea(CRI Project No.2018R1A3B1052702 for Jong Seung Kim)。

摘　　要：Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners.External electric fields(EEFs)can influence the reactivity and selectivity of the substrate by causing directional adsorption.However,scalable and efficient techniques for using EEFs as“smart catalysts”have been lacking,hindering their application.In this study,we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer(EDL)theory.This approach led to moderate to good yields of the corresponding C7-thiocyanation products.DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones,allowing the C7-thiocyanation to proceed via a radical reaction mechanism.Additionally,the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties.Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.

关 键 词：electric fields reaction-axis rule electric double layer C7-thiocyanation C-S bond formation 

分 类 号：O621.25[理学—有机化学]