Para-selective borylation of monosubstituted benzenes using a transient mediator  

作　　者：Jie Wu Zengwei Wang Xiao-Yue Chen Yichen Wu Daoming Wang Qian Peng Peng Wang 

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,Shanghai 200032,China [2]CAS Key Laboratory of Energy Regulation Materials,Shanghai Institute of Organic Chemistry,Shanghai 200032,China [3]State Key Laboratory of Elemento-Organic Chemistry,College of Chemistry,Nankai University,Tianjin 300071,China

出　　处：《Science China Chemistry》2020年第3期336-340,共5页中国科学（化学英文版）

基　　金：supported by Shanghai Institute of Organic Chemistry,State Key Laboratory of Organometallic Chemistry,the National Natural Science Foundation of China(21890722,21702109,11811530637);the Natural Science Foundation of Tianjin City(18JCYBJC21400);the Fundamental Research Funds for the Central Universities(63191515,63196021,63191523).

摘　　要：Herein,we conceptualized a transient mediator approach that has the capability of para-selective C–H functionalization of monosubstituted aromatics.This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride.Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate.The versatility of this approach was demonstrated via paraborylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.Herein,we conceptualized a transient mediator approach that has the capability of para-selective C–H functionalization of monosubstituted aromatics.This approach is enabled by in situ generation of a versatile sulfonium salt via highly electrophilic phenoxathiine or thianthrene dication intermediate which can be readily generated from its sulfoxide with trifluoromethanesulfonic anhydride.Preliminary mechanistic study implied that the remarkable para selectivity might be related to the incredible electrophilicity of thianthrene dication intermediate.The versatility of this approach was demonstrated via paraborylation of various monosubstituted simple aromatics combining the sulfonium salt formation with further photocatalyzed transformation.

关 键 词：para-borylation monosubstituted ARENE TRANSIENT MEDIATOR thianthrenation sulfide DICATION 

分 类 号：O621.25[理学—有机化学]