Organic molecules containing gem-difluoromethylene unit are one of the most important classes of compounds that have var-ious valuable applications ranging from drug discovery to mate-rial science[1].Not surprisingly,numerous strategies have been developed towards the synthesis of these target organofluorine compounds.Within this research area,direct C-F bond cleavage of cheap and readily accessible polyfluorinated compounds repre-sents one of the most potentially powerful methods to access di-verse gem-difluoromethylene skeletons.Compared with the well developed ionic types of C-F bond cleavage processes[2],deflu-orinative functionalization CF3 groups via the formation of fluo-roalkyl radicals is relatively overlooked.Recent synthetic efforts us-ing photochemical strategy mainly focused on the Ar-CF3 systems,in which single-electron reductive generation of arene radical an-ion followed by a fluoride anion elimination was proposed as the key step to form the fluoroalkyl radicals[3-9].However,the re-quirement of electron-deficient substituents(generally-CN group)on trifluoromethylarenes and the relatively low synthetic value of the formed benzylic gem-difluoromethylene products limited the method for further application.Wang and Houk recently expanded the reaction substrates to selective C-F bond cleavage of trifluo-roacetamides and acetates via a boryl radical enabled spin-center shift(SCS)strategy[10].Despite high efficiency,the harsh reac-tion conditions(stoichiometric DTBP,high reaction temperature)still left space for the exploration of alternative green and mild re-action systems.

Zele Chen;Jiarong Chen;Jun Xuan

Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province,College of Chemistry&Chemical Engineering,Anhui University,Hefei 230601,China;CCNU-uOttawa Joint Research Centre,College of Chemistry,Central China Normal University,Wuhan 430079,China

中国化学快报（英文版）

[1]Zele Chen;Jiarong Chen;Jun Xuan-.Photochemical defluorinative functionalization of α-poly fluorinated carbonyls via spin-center shift)[J].中国化学快报（英文版）,2022(06):2763-2764

difluoromethylene,organofluorine,polyfluorinated,deflu,orinative,roalkyl,fluoroalkyl,trifluoromethylarenes,Houk,trifluo,roacetamides,acetates

Photochemical,defluorinative,functionalization,carbonyls,via,spin,center,shift,Organic,molecules,containing,gem,unit,one,most,important,classes,compounds,that,have,var,ious,valuable,applications,ranging,from,drug,discovery,mate,rial,science,Not,surprisingly,numerous,strategies,been,developed,towards,synthesis,these,target,Within,this,research,area,direct,bond,cleavage,cheap,readily,accessible,repre,sents,potentially,powerful,methods,verse,skeletons,Compared,well,ionic,types,processes,CF3,groups,formation,radicals,relatively,overlooked,Recent,synthetic,efforts,photochemical,strategy,mainly,focused,Ar,systems,which,single,electron,reductive,generation,followed,by,fluoride,anion,elimination,was,proposed,key,step,However,quirement,deficient,substituents,generally,CN,value,formed,benzylic,products,limited,further,Wang,recently,expanded,reaction,substrates,selective,boryl,enabled,SCS,Despite,high,efficiency,harsh,conditions,stoichiometric,DTBP,temperature,still,left,space,exploration,alternative,green,mild

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