Aromatic Metamorphosis of Dibenzofurans into Triphenylenes Starting with Nickel-Catalyzed Ring-Opening C-O Arylation.

A new class of aromatic metamorphosis has been developed in which dibenzofurans were converted into triphenylenes. This transformation is composed of three successive operations: (1) nickel-catalyzed ring-opening C-O bond arylation with arylmagnesium bromides, (2) trifluoromethanesulfonylation (triflation) of the resulting hydroxy moiety with Tf2O, and (3) palladium-catalyzed or photoinduced ring closure. In the last ring-closing step, the photoinduced process has proven to be more productive than the palladium-catalyzed one. By employing π-extended dinaphthofuran as the substrate, dorsally benzo-fused [5]helicene was obtained in a satisfactory yield.