Synthesis of Polyfluoroalkyl Aza-Polycyclic Aromatic Hydrocarbons Enabled by Addition of Perfluoroalkyl Radicals onto Vinyl Azides

Radical perfluoroalkylation of α-(biaryl-2-yl)­vinyl azides is capable of supplying polyfluoroalkyl aza-polycyclic aromatic hydrocarbons (aza-PAHs). Commercially available Me₃SiR_f (R_f = CF₃, C₂F₅, and C₃F₇) are employed as the sources of perfluoroalkyl radicals upon oxidation with PhI­(OAc)₂. The addition of perfluoroalkyl radicals to biarylvinyl azides generates the corresponding iminyl radicals, which subsequently cyclize with the intramolecular arene moiety, furnishing aza-PAH skeletons having polyfluoroalkyl (R_fCH₂) function.