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.
Song et al. (Sat,) studied this question.