Transition‐Metal‐Free Coupling of Polyfluorinated Arenes and Functionalized, Masked Aryl Nucleophiles

A chemoselective C(sp(2))−C(sp(2)) coupling of sufficiently electron‐deficient fluorinated arenes and functionalized N‐aryl‐N’‐silyldiazenes as masked aryl nucleophiles is reported. The fluoride‐promoted transformation involves the in situ generation of the aryl nucleophile decorated with various sensitive functional groups followed by a stepwise nucleophilic aromatic substitution (S(N)Ar). These reactions typically proceed at room temperature within minutes. This catalytic process allows for the functionalization of both coupling partners, furnishing highly fluorinated biaryls in good yields.