Decatungstate‐Mediated C(sp³)–H Heteroarylation via Radical‐Polar Crossover in Batch and Flow

Photocatalytic hydrogen atom transfer is a very powerful strategy for the regioselective C(sp³)–H functionalization of organic molecules. Herein, we report on the unprecedented combination of decatungstate hydrogen atom transfer photocatalysis with the oxidative radical–polar crossover concept to access the direct net‐oxidative C(sp³)–H heteroarylation. The present methodology demonstrates a high functional group tolerance (40 examples) and is scalable when using continuous‐flow reactor technology. The developed protocol is also amenable to the late‐stage functionalization of biologically relevant molecules such as stanozolol, (−)‐ambroxide, podophyllotoxin, and dideoxyribose.