Photochemical defluorinative functionalization of α-poly fluorinated carbonyls via spin-center shift
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.
shift、poly、carbonyls、defluorinative、fluorinated、functional、photochemical、spin-center
33
TP391;TN391;TP751
2022-07-20（万方平台首次上网日期，不代表论文的发表时间）
共2页
2763-2764
