Nitromethane-Enabled Fluorination of Styrenes and Arenes

The electrophilic fluorination of unsaturated compounds provides a reliable approach to the generation of organofluorides,which are used widely in agrochemicals,pharmaceuticals,and other materials.Numerous active electrophilic fluorine reagents,such as the fluorine molecule(F_(2))or xenon difluoride(XeF_(2)),have been applied in fluorination.However,these reagents suffer from their hazardous,toxic,corrosive,and poor selective properties,and the relatively weak electrophilicity of Selectfluor or N-fluorobenzenesulfonimide(NFSI)usually limits their broad applications.Herein,we disclose nitromethane(MeNO_(2))as an efficient activator of Selectfluor and NFSI,as well as a stabilizer of carbocations.Therefore,the fluoro-azidation,fluoroamination,fluoroesterification of styrenes,and C–H fluorination of(hetero)arenes were well realized just by the facilitation of MeNO_(2).The mild reaction conditions and practicability made our current method a versatile protocol for accessing organofluorides.