Data and code availability
Data relating to the materials and methods, experimental procedures, nuclear magnetic resonance (NMR) spectra, and analytical data of the compounds generated in this study are provided in the supplemental information.
Over the past decades, considerable efforts have been devoted toward exploring readily available trifluoroacetic acid or its anhydride as a CF3 source for trifluoromethylation reactions. Herein, a general photocatalytic method was developed for fluoroalkylation of arenes and aromatic heterocycles with fluoroalkyl carboxylic anhydrides using simple acetoxime as the activator. The established conditions were also applicable to oxytrifluoromethylation and intramolecular carbotrifluoromethylation of alkenes, and the modification of biologically active molecules and gram-scale synthesis further highlighted its potential utility. Compared with the fact that single-electron transfer (SET) reduction of oxime trifluoroacetate esters generates preferentially iminyl radical and stable trifluoroacetate anions, our work discovered the unprecedented acid-triggered reactivity umpolung of acetoxime ester toward delivering a CF3 radical.
Data relating to the materials and methods, experimental procedures, nuclear magnetic resonance (NMR) spectra, and analytical data of the compounds generated in this study are provided in the supplemental information.