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

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), whic...

Descripción completa

Detalles Bibliográficos
Autores: Rodiño Balboa, Ricardo, Mascareñas Cid, José Luis, López García, Fernando José
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universidad de Santiago de Compostela (USC)
Repositorio:Minerva. Repositorio Institucional de la Universidad de Santiago de Compostela
Idioma:inglés
OAI Identifier:oai:minerva.usc.gal:10347/42449
Acceso en línea:https://hdl.handle.net/10347/42449
Access Level:acceso abierto
Palabra clave:Alkylidenecyclopropane
Palladium
Cycloaddition
Dipole
Zwitterionic
Phosphoramidite
Descripción
Sumario: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.