Álvarez Pérez, BertaJaneiro, JesúsCobas Martínez, AgustínOrtuño Maqueda, Manuel ÁngelPeña Gil, DiegoGuitián Rivera, EnriquePérez Meirás, María Dolores2024-04-242024-04-242024B. Álvarez, J. Janeiro, A. Cobas, M. A. Ortuño, D. Peña, E. Guitián, D. Pérez, Adv. Synth. Catal. 2024, 366, 961. https://doi.org/10.1002/adsc.2023012641615-4150http://hdl.handle.net/10347/33648A previously undescribed aryne derived from a π-extended biphenylene, 2,3-didehydrobenzo[b]biphenylene, has been developed. The participation of this new aryne building block in [4+2] and palladium-catalyzed [2+2+2] cycloaddition reactions has been applied to the synthesis of a variety of polycyclic conjugated hydrocarbons (PCHs) with appealing structures which combine (aromatic) benzene and (antiaromatic) cyclobutadiene (CBD) rings. Among them, a family of unsubstituted (or barely substituted) CBD-oligoacenes has been accessed by iterative Diels-Alder reactions of the new aryne with furans and/or isobenzofurans, followed by deoxygenative aromatization of the resulting epoxy-derivatives. The experimental and computational studies of the newly synthesized PCHs suggest an important degree of electron delocalization along the polycyclic skeleton, more pronounced in the linearly fused derivatives. The computed ACID plots reveal clockwise current density vectors at the peripheral bonds, originating from the σ contributions of the antiaromatic cyclobutadiene rings.engAttribution-NonCommercial-NoDerivatives 4.0 Internacional© 2024 The Authors. Advanced Synthesis & Catalysis published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial NoDerivs License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non-commercial and no modifications or adaptations are made.http://creativecommons.org/licenses/by-nc-nd/4.0/Polycyclic conjugated hydrocarbonsArynesCycloaddition reactionsBiphenyleneCyclobutadiene containing oligoacenesjournal article10.1002/adsc.2023012641615-4169open access