Domino Dehydrative π‐Extension: A Facile Path to Extended Perylenes and Terrylenes

Herein, we report a new method for synthesis of extended perylenes and terrylenes. The technique is based on the cascade dehydrative π‐extensions (DPEX) of aryl aldehydes, in which stepwise annulations activate previously “dormant” substituents. Two‐ and fourfold cyclizations of 3‐aryl‐biphenyl‐2,2′‐dicarbaldehydes offer a rapid path to unsymmetrical perylenes and elusive terrylene derivatives, respectively. DPEX of 3,3′′‐(phenanthrene‐1,8‐diyl)bis (([1,1′‐biphenyl]‐2,2′‐dicarbaldehyde)) leads to the biradical structure, which proceeds in situ into oxidative electrocyclization at room temperature. The described domino process complements and expands DPEX approach to a large family of fused acenes and related PAHs.