Pentacoordinate Phosphoranes as Versatile Reagents in Fluoroalkylation Reactions  

作　　者：Huanhuan Song Weihao Li Xiaoying Wang Kaiteng Wang Jingwen Li Shuai Liu Pin Gao Xin-Hua Duan Jinbo Hu Mingyou Hu 

机构地区：[1]School of Chemistry,Engineering Research Center of Energy Storage Materials and Devices,Ministry of Education,Xi’an Key Laboratory of Sustainable Energy Material Chemistry,Xi’an Jiaotong University,Xi’an 710049 [2]Key Laboratory of Organofluorine Chemistry,Center for Excellence in Molecular Synthesis,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032

出　　处：《CCS Chemistry》2024年第1期165-176,共12页中国化学会会刊（英文）

基　　金：supported by National Natural Science Foundation of China(grant no.21901196);the Natural Science Basic Research Plan in Shaanxi Province of China(grant nos.2020JQ-016 and 2021GXLH-Z-096);the Fundamental Research Funds for the Central Universities(grant no.xhj032021007-01);Xi’an Jiaotong University(grant no.71211920000001).

摘　　要：A general method for the synthesis of bench-stable bis(difluoromethyl)pentacoordinate phosphoranes has been developed.The reaction is rapid,operationally simple,and easily scalable.The pentacoordinate phosphoranes can generate both difluoromethyl radical(·CF_(2)H)and difluorocarbene(:CF_(2))intermediates.Thus,a variety of fluoroalkylation transformations havebeen achieved by·CF_(2)H,such asoxidativedifluoromethylation of electron-deficient heterocycles,nickel/photoredox dual-catalyzed difluoromethylation of aryl bromides,and photoredox difluoromethylation of alkenes,or by:CF_(2),such as gem-difluorocyclopropanation of alkenes,base-promoted difluoromethylation of heteroatom nucleophiles,Pd-catalyzed difluoromethylation of arylboronic acids,and Cu-mediated trifluoromethylation of aryl iodides(via:CF_(2) and recombined CF_(3)-).These fluoroalkylation methods have been successfully applied to late-stage fluoroalkylation of drugs and drug-like molecules.

关 键 词：pentacoordinate phosphorane difluoromethyl radical DIFLUOROCARBENE DIFLUOROMETHYLATION FLUOROALKYLATION 

分 类 号：O62[理学—有机化学]