Synthesis of 2,24-Diene-12,13,15,16,34,35,37,38-octaphenyl[4.4]triphenylparacyclophane

Abstract

A new octaphenyl[4.4]triphenylparacyclophanediene was readily synthesized in six steps from p-xylene via the installment of bromine atoms, replacement with a vinyl group, carbonylative coupling, intermolecular followed by intramolecular double Grubbs olefin metathesis, Knoevenagel condensation, and Diels–Alder cycloaddition. The belt-shaped structure and trans-stereochemistry of the alkene moieties of the octaphenyl[4.4]triphenylparacyclophane and a synthetic intermediate, 2,21-dioxo-11,30-diene[3.4.3.4]paracyclophane, were determined by X-ray crystallography. The synthetic methodology leading to octaphenyl[4.4]triphenylparacyclophane is applicable for the synthesis of substituted triphenylparacyclophanes and possibly their corresponding bis-hexabenzocoronenylparacyclophanes via a Scholl–Mullen oxidative aryl-aryl coupling reaction.

Key words

belt-shaped molecules - cyclophanes - octaphenyl[4.4]triphenylparacyclophane - Grubbs olefin metathesis - Knoevenagel condensation­ - Diels–Alder cycloaddition - carbonylative coupling

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