Cooperative NHC/Photoredox Catalyzed Ring‐Opening of Aryl Cyclopropanes to 1‐Aroyloxylated‐3‐Acylated Alkanes

Cyclopropanes are an important class of building blocks in organic synthesis. Herein, a ring‐opening/arylcarboxylation/acylation cascade reaction for the 1,3‐difunctionalization of aryl cyclopropanes enabled by cooperative NHC and organophotoredox catalysis is reported. The cascade works on monosubstituted cyclopropanes that are in contrast to the heavily investigated donor–acceptor cyclopropanes more challenging to be difunctionalized. The key step is a radical/radical cross coupling of a benzylic radical generated in the photoredox catalysis cycle with a ketyl radical from the NHC catalysis cycle. The transformation features metal‐free reaction conditions and tolerates a diverse range of functionalities.