Palladium‐Catalyzed [3+2+2] Cycloaddition Between Carbonyl‐Tethered Alkylidenecyclopropanes and Isocyanates
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.
Authors
- Ricardo Rodiño (ORCID: https://orcid.org/0000-0002-3419-5294)
- José L. Mascareñas (ORCID: https://orcid.org/0000-0002-7789-700X)
- Fernando López (ORCID: https://orcid.org/0000-0002-0235-6858)
Institutions
- Consejo Superior de Investigaciones Científicas (ES)
- Universidade de Santiago de Compostela (ES)
- Misión Biológica de Galicia (ES)
- Center for Research in Molecular Medicine and Chronic Diseases (ES)
Publication Details
- Journal
- Helvetica Chimica Acta
- Published
- 2025-02-20
- DOI
- https://doi.org/10.1002/hlca.202500011
- Citations
- 1
- Primary Topic
- Cyclopropane Reaction Mechanisms
- Type
- article
- Field-Weighted Citation Impact
- 0.94
Funders
- European Commission
- Centro Singular de Investigación de Galicia
- Instituto de Salud Carlos III
- European Regional Development Fund
- Agencia Estatal de Investigación