Chemoselective electrochemical seleno-cyclization of dienes to medium-sized benzo[b]azocines  

作　　者：Zhichuan Wang Xin Wang Quanxin Li Shaofei Ni Dongyang Zhao Shubin Yang Ge Qiu Kai Sun 

机构地区：[1]College of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China [2]Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province,Shantou University,Shantou 515063,China [3]Aix Marseille Univ.,CNRS,Centrale Marseille,iSm2,Marseille,France

出　　处：《Chinese Chemical Letters》2024年第2期431-435,共5页中国化学快报（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.21801007);Qingchuang Technology Support Program of University in Shandong Province(No.2021KJ066);S.-F.Ni acknowledges funding from the STU Scientific Research Foundation for Talents(No.NTF20022).

摘　　要：The preparation of medium-sized benzo[b]azocines has always been challenging because of inherently unfavorable enthalpy and entropy factors.This report presents a novel approach for accessing 8-membered seleno-benzo[b]azocines via electrochemically-driven seleno-cyclization.This method enables room-temperature preparation of various structurally diverse medium-sized seleno-benzo[b]azocines.The facile deselenation of the seleno-cyclization products to generate functionalized dienes is an additional benefit of this indispensable reaction.Mechanistic insights are presented based on radical inhibition experiments and cyclic voltammetry measurements,which elucidate the radical pathway.Finally,density functional theory calculations further rationalize the rate-determining step and the unique chemoselectivity observed in this transformation.

关 键 词：Medium-sized n-heterocycles ELECTROCATALYSIS Radical Mechanistic insights Selenylation 

分 类 号：TQ25[化学工程—有机化工]