Decoupling Radical Generation and Copper Catalysis for the Remote C–H Cyanation of Unfunctionalized Sulfonamides

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A decoupled photoredox/copper dual catalytic system for the remote C(sp 3 )–H cyanation of aliphatic sulfonamides is described. The strategy circumvents the need for substrate prefunctionalization, a limitation of previous “coupled” systems. An acridinium photocatalyst generates a nitrogen radical from a free N–H bond, while an independent copper cycle, sustained by an external oxidant, forges the C–CN bond with high δ-selectivity.