Photoredox and CO 2 -Catalyzed Deep Skeletal Remodeling Via Merged C–H and C–C Bond Cleavages

Abundant C–H and C–C bonds can undergo homolytic cleavage through radical processes, enabling the subsequent formation of new C–C bonds that profoundly reshape molecular architectures. Yet, merging these distinct elementary steps into a single catalytic blueprint capable of achieving full skeletal reorganization has remained highly challenging due to the complex orchestration of the intricate sequence. Herein, we report a photoredox-catalyzed C–H alkylation intricately coupled to a round-trip radical cascade that delivers a striking skeletal remodeling of cyclopropyl alkanols. The use of a carbon dioxide atmosphere proves essential for ensuring the reaction efficiency and expanding the reaction scope. Mechanistic studies uncover that in situ generated catalytic salts play a decisive role in choreographing the radical cascade and enabling key steps of the transformation.