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Phenyl-substituted tetra-, penta-, hexa- and octacenes were easily obtained starting from a readily available naphthalene-based bisaryne precursor. This approach to large acenes involves a sequence of two Diels–Alder cycloadditions with dienones followed by two CO extrusion reactions.

Graphical abstract: Large phenyl-substituted acenes by cycloaddition reactions of the 2,6-naphthodiyne synthon

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