Three‐Component Defluorinative Annulation of Polyfluoroalkyl Tetralones, Amidines, and Cobalt‐Dionates: Synthesis of Fluoro‐Alkyl 4‐(furan‐2‐yl)quinazolines

An unprecedented defluorinative multicomponent reaction of polyfluoroalkyl ketones, amidines, and cobalt‐dionates is developed for the modular synthesis of structurally unique fluoroalkyl 4‐(furan‐2‐yl)quinazolines. The reaction proceeds through selective activation of six aliphatic CF bonds on three sterically congested polyfluoroalkylcarbon sites, therefore eliminating the classical reliance on multistep prefunctionalization and transition‐metal‐catalyzed couplings. Cobalt‐dionates are used as versatile 1,3‐dicarbonyl surrogates in the [3 + 2]‐annulation, wherein key fluoroalkenyl intermediates are involved. Moreover, the reaction features good compatibility with various functional groups and applicability in postfunctionalization of the resulting heteroaromatics.