Photoinduced Electron Donor–Acceptor Complex‐Enabled Tandem Perfluoroalkylation/Cyclization of Internal Alkenes Toward Ring‐Fused Quinazolinones

N ‐(3‐Methylbut‐2‐en‐1‐yl)quinazolin‐4(3 H )‐ones were designed as novel skeletons to provide C2‐perfluoroalkylated pyrrolo‐quinazolin‐4(3 H )‐ones in moderate to excellent yields through electron donor–acceptor (EDA) complex‐triggered tandem perfluoroalkylation/cyclization with commercially available perfluoroalkyl iodides. Moreover, the construction of C3‐perfluoroalkylated piperidino‐quinazolinones was also achieved through the EDA complex‐promoted perfluoroalkylation/cyclization of N ‐(4‐methylpent‐3‐en‐1‐yl)quinazolin‐4(3 H )‐ones. In those reactions, the perfluoroalkyl group was directly installed into the heterocyclic ring cores instead of the side chains.