Photocatalytic Reductive Azaarenylation of Cyclopropanes via Consecutive Photo‐induced Electron Transfer: A Facile Route to α‐Quaternary Azaarenes†

Comprehensive Summary α‐Azaarene quaternary carbon centers are prevalent in drug molecules, making the development of efficient synthetic approaches of great interest. Herein, we describe an unprecedented method for constructing α‐all‐carbon quaternary carbon‐centered azaarenes by employing photocatalytic reductive coupling of various 2,2‐disubstituted cycloproarylketones with readily available cyanoazaarenes. The reaction proceeds with high efficiency, displaying excellent compatibility with various functional groups and demonstrating high chemo‐ and regioselectivity. Mechanistic investigations suggest that consecutive photo‐induced electron transfer (ConPET) plays a crucial role in the formation of photocatalyst with greater reducing capability, ultimately enabling the direct reductive conversion of unreactive π‐bonds under mild and transition‐metal‐free conditions.