Predictable site-selective radical fluorination of tertiary ethers  

作　　者：Junyang Ma Wentao Xu Jin Xie 

机构地区：[1]State Key Laboratory of Coordination Chemistry,Jiangsu Key Laboratory of Advanced Organic Materials,Chemistry and Biomedicine Innovation Center,School of Chemistry and Chemical Engineering,Nanjing University

出　　处：《Science China Chemistry》2020年第2期187-191,共5页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(21971108,21702098);the Natural Science Foundation of Jiangsu Province(BK20190006);Fundamental Research Funds for the Central Universities(020514380176);“Jiangsu Six Peak Talent Project”;“1000-Youth Talents Plan’’;start-up funds from Nanjing University;supported by the Scientific Research Foundation of Graduate School of Nanjing University(2018CL05)

摘　　要：In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols.In this communication,we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers,enabled by synergistic photocatalysis and organocatalysis.This catalytic combination allows for exclusive fluorination of tertiary C–O bonds under mild conditions even in the presence of competing reaction sites.The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules.The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols.

关 键 词：cooperative catalysis C–O bond activation radical fluorination polarity-matching effect UMPOLUNG 

分 类 号：O621.251[理学—有机化学]