Selective C–O bond formation via a photocatalytic radical coupling strategy: access to perfluoroalkoxylated (OR(F)) arenes and heteroarenes

Development of an efficient process that employs commercially available and cost effective reagents for the synthesis of perfluoroalkoxylated aromatic compounds (Ar–OR(F)) remains a daunting challenge in organic synthesis. Herein, we report the first catalytic protocol using readily available perfluoroalkyl iodides (R(F)I) and N-(hetero)aryl-N-hydroxylamides to access a wide range of perfluoroalkoxylated (hetero)arenes. Mild reaction conditions allow for selective O–R(F) bond formation over a broad substrate scope and are tolerant of a wide variety of functional groups. Mechanistic studies suggest the formation and recombination of persistent N-hydroxyl radicals and transient R (F) radicals under photocatalytic reaction conditions to generate N–OR(F) compounds that rearrange to afford the desired products.