Polycyclic heteroaromatic ring construction driven by silver/cobalt co-catalyzed desulfonylative and defluorinative fragment-recombination of enol nonaflates with amidines.

We present a Ag(i)/Co(ii) co-catalyzed tandem fragmentation and recombination reaction commencing from detachable nonaflates and amidines. This catalytic method offers a unique and expeditious access to various fluoroalkylated dihydrobenzo[h]quinazolines and benzo[h]quinazolines in the absence of external fluorine sources through a rationally designed radical desulfonylation, migration, defluorination, and polar condensation relay.