Palladium-Catalyzed [3+2+2] Cycloaddition Between Carbonyl-Tethered Alkylidenecyclopropanes and Isocyanates

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URI: https://hdl.handle.net/10347/42449
ISSN: 0018-019X
ISSN: 10.1002/hlca.202500011
E-ISSN: 1522-2675

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2025-02-20

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Wiley
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Abstract

Carbonyl-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.

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Alkylidenecyclopropane| Palladium| Cycloaddition| Dipole| Zwitterionic| Phosphoramidite

Bibliographic citation

R. 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.202500011

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This work received financial support from Spanish grants (Grants PID2020-118579GB-I00, PID2022-137318OB-I00 and PID2023-152054NB-100, funded by MCIN/AEI, Grant IHRC22-00009 funded by MCIN/ISCIII and by the “European Union NextGenerationEU/PRTR”, the ORFEO-CINQA network RED2022-134287-T and a predoctoral fellowship to R. R.), the Consellería de Cultura, Educación e Ordenación Universitaria (Grant ED431C 2021/25 and Grant ED431G 2019/03: Centro Singular de Investigación de Galicia accreditation 2023–2027, ED431G 2023/03) and the European Union (European Regional Development Fund-ERDF).

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© 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.
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