Photomediated Solvent-Switched Direct C–H Arylation vs Oxyalkylation of Azauracils Using Unactivated Aryl Iodides

Herein, we report a unified, photoinduced, solvent-controlled strategy for two distinct C–H functionalizations of azauracils: arylation in DMSO and oxyalkylation in THF via direct homolytic cleavage of the C–I bond of photoexcited aryl iodides. Mechanistic studies revealed a dual role of aryl iodides, serving as arylating agents in DMSO and hydrogen atom transfer (HAT) mediators with cyclic ethers, thus facilitating divergent C(sp2)–H and C(sp3)–H functionalizations. The protocol exhibited broad substrate compatibility and is amenable to scale-up and late-stage functionalization.