Oxidative Intramolecular C-C Bond Formation Reactions of 1,2-Diarylbenzenes: Syntheses of Highly Conjugated Double-Bridged Polycyclic Aromatic Hydrocarbons

Oxidation reactions of 1,2-diarylbenzenes induce intramolecular C-C bond formation. The substrates studied here were prepared by the stepwise Suzuki-Miyaura coupling reaction that introduced 2-naphthyl, 2-anthranyl, and 2-pyrenyl groups on the ortho positions of benzene. The subsequent oxidation reaction with FeCl3 induced an oxidative C-C bond formation reaction in the interior regions of the molecules. In marked contrast to our previous observations, two C-C bonds were formed. Theoretical calculations indicated that large spin densities at the reaction positions of the bis(cation radical) and/or cation radical species are needed for the C-C bond formation. The π-expanded molecules obtained here showed bathochromic shifts in the absorption spectra and amphoteric multi-redox behavior in electrochemistry.