Introducing 1,3-enyne functionalization by nitrene transfer reaction

In the context of carbon–nitrogen bond formation, metal-catalyzed nitrene transfer reactions constitute a powerful transformation. While many saturated and unsaturated substrates can be modified with this strategy, the incorporation of nitrene into enynes yet remains undescribed. Herein, we report t...

Descripción completa

Detalles Bibliográficos
Autores: Rodriguez, Anabel M., Sciortino, Giuseppe, Munoz-Gutierrez, Lidia, Molina, Francisco, Maseras, Feliu, Diaz-Requejo, M. Mar, Perez, Pedro J.
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2024
País:España
Institución:Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya)
Repositorio:Recercat. Dipósit de la Recerca de Catalunya
OAI Identifier:oai:recercat.cat:2072/537495
Acceso en línea:http://hdl.handle.net/2072/537495
https://doi.org/10.1016/j.checat.2023.100865
Access Level:acceso abierto
Palabra clave:Química
54
Descripción
Sumario:In the context of carbon–nitrogen bond formation, metal-catalyzed nitrene transfer reactions constitute a powerful transformation. While many saturated and unsaturated substrates can be modified with this strategy, the incorporation of nitrene into enynes yet remains undescribed. Herein, we report the first example of this transformation, leading to the formation of propargyl aziridines or unsaturated sulfinamides, corresponding to the attack of a copper-nitrene intermediate onto the ene or yne sites. Density functional theory (DFT) studies have provided an explanation for this diverse reactivity, which is sustained on the interactions of the enyne substituent with the pyrazolyl rings of the trispyrazolylborate ancillary ligand of the catalyst.