Castro Esteban, JesúsAlbrecht, FlorianFatayer, ShadiPérez Meirás, María DoloresGross, LeoPeña Gil, Diego2022-08-112022-08-112021Angew. Chem. Int. Ed. 2021, 60, 26346 – 26350. https://doi.org/10.1002/anie.2021103111433-7851http://hdl.handle.net/10347/29052The Diels–Alder reaction is one of the most popular reactions in organic chemistry. However, its use in the field of on-surface synthesis is hampered by the spatial restrictions of this cycloaddition reaction. Herein we selected a cyclic strained triyne to demonstrate an on-surface hexadehydro-Diels–Alder reaction in a single molecule. The reaction was studied in detail by means of atomic force microscopy (AFM) with CO-functionalized tips. Our results pave the way to use this iconic pericyclic reaction for on-surface synthesis, introducing the concept of atom economy in the fieldeng©2021 The Authors. Angewandte Chemie International Edition 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 noncommercial and no modifications or adaptations are madehttp://creativecommons.org/licenses/by-nc-nd/4.0/Bond-resolved AFMCycloadditionDiels–Alder reactionOn-surface synthesisPolycyclic aromatic hydrocarbonsjournal article10.1002/anie.2021103111521-3773open access