A cascade carbene insertion reaction on recoverable catalytic metal-free zeolites

[EN] The generation and insertion reaction of carbenes is incompatible with strong oxidants or highly basic amino groups due to the rapid deactivation of the metal catalysts necessary to generate the carbenes. Here, we show that dealuminated zeolites are capable not only of generating and inserting...

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Detalles Bibliográficos
Autores: Espinosa, Miguel, Zheng, Yongkun, Ceron-Carrasco, Jose Pedro, Martínez-Belenguer, Lluis, Leyva Perez, Antonio|||0000-0003-1063-5811
Tipo de recurso: artículo
Fecha de publicación:2025
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/230286
Acceso en línea:https://riunet.upv.es/handle/10251/230286
Access Level:acceso abierto
Palabra clave:Carbene insertion
Diazoacetates
Dealuminated zeolites
One-pot catalysis
Cascade reactions
Heterogeneous catalysis
Descripción
Sumario:[EN] The generation and insertion reaction of carbenes is incompatible with strong oxidants or highly basic amino groups due to the rapid deactivation of the metal catalysts necessary to generate the carbenes. Here, we show that dealuminated zeolites are capable not only of generating and inserting carbenes from diazoacetates into O-H bonds, but also of allowing the in situ dehydrogenation reaction of the so-generated alcohol with (hydro)peroxides and the subsequent imination/isomerization (for non-aromatic imines) of the resulting ketoester with a primary amine, all in a one-pot catalytic mode. In this way, a variety of alpha-iminoesters can be generated from diazoacetates, water (also in catalytic amounts), and amines, with a recoverable and reusable solid catalyst. These results open the possibility of telescoping a carbene-mediated reaction with classical oxidation and condensation reactions in a cascade fashion, under the action of a simple and commercially available solid catalyst.