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

Abstract

Oxidation reactions of 1,2-diarylbenzenes induce intramolecular C–C bond formation. The substrates studied 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 showed bathochromic shifts in the absorption spectra.

Key words

polycyclic aromatic hydrocarbon - oxidative C–C bond formation - FeCl₃ - pyrene - naphthalene - anthracene

Publication History

Received: 30 June 2021

Accepted after revision: 28 July 2021

Accepted Manuscript online:
28 July 2021

Article published online:
22 September 2021

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