Light-assisted functionalization of aryl radicals towards metal-free cross-coupling

The many synthetic possibilities that arise when using radical intermediates, in place of their polar counterparts, make contemporary radical chemistry research an exhilarating field. The introduction of photocatalysis has helped tame aryl radicals, leading to a resurgence of interest in their chemistry, and an expansion of viable coupling partners and attainable transformations. These methods are more selective and safer than classical approaches, and they utilize new radical precursors. Given the importance of sustainability in current organic synthesis and our interest in light-assisted metal-free transformations, this Review focuses on recent advances in the use of aryl radicals in photoinduced cross-couplings that do not rely on metals for the crucial bond-forming event, and it is structured according to the key step that the aryl radicals engage in.