Mechanoradical-driven C–H halogenation and nitration of arenes and vicinal dibromination of alkenes in the solid state

Abstract

We report a solvent-free mechanochemical approach for the C–H halogenation and nitration of arenes. In situ-generated oxygen-centered mechanoradicals readily oxidize halide or nitrite salts, enabling C–H functionalization of arenes. Radical trapping experiments confirm the involvement of bromine radical species, distinct from conventional solution-phase processes that predominantly proceed via brominium intermediates. This operationally simple and carbon-free strategy is further extended to solid-state vicinal dibromination reactions of unactivated alkenes.