Rodiño Balboa, RicardoMascareñas Cid, José LuisLópez García, Fernando José2025-07-112025-07-112025-02-20R. Rodiño, J. L. Mascareñas, F. López, Palladium-Catalyzed [3+2+2] Cycloaddition Between Carbonyl-Tethered Alkylidenecyclopropanes and Isocyanates. Helv. Chim. Acta 2025, 108, e202500011. https://doi.org/10.1002/hlca.2025000110018-019X10.1002/hlca.202500011https://hdl.handle.net/10347/42449Carbonyl-tethered alkylidenecyclopropanes can react with aryl isocyanates in presence of Pd(0)-phosphoramidite catalysts to give seven-membered heterobicyclic products in a formal [3+2+2] cycloaddition process. The reaction involves the formation of a palladium π-allyl complex intermediate (A), which behaves as a formal 1,5-dipole, and can be trapped by externally added isocyanates. This report also includes preliminary assays of asymmetric variants, as well as DFT computational studies that shed some light on the nature of the catalytic cycle.eng© 2025 The Author(s). Helvetica Chimica Acta published by Wiley-VHCA AG. This is an open access article under the terms of the Creative Commons Attribution Non-Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.Attribution-NonCommercial 4.0 Internationalhttp://creativecommons.org/licenses/by-nc/4.0/AlkylidenecyclopropanePalladiumCycloadditionDipoleZwitterionicPhosphoramiditejournal article1522-2675open access