Methane Catalytic Amidation via a Plausible Copper-Nitrene Intermediate

The catalytic conversion of CH4 into CH3X compounds has been reported in a few cases, usually involving dehydrogenative processes in which the H atom is lost. Aiming at expanding this limited set of transformations, we have investigated the methane amidation reaction through metal-catalyzed nitrene...

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Detalles Bibliográficos
Autores: Martínez Laguna, Jonathan, Cholewinska, Anna, Borrego, Elena, Besora, María, Álvarez, María, Caballero Bevia, Ana, Pérez Romero, Pedro José
Tipo de recurso: artículo
Fecha de publicación:2026
País:España
Institución:Universidad de Huelva (UHU)
Repositorio:Arias Montano. Repositorio Institucional de la Universidad de Huelva
Idioma:inglés
OAI Identifier:oai:dnet:ariasmontano::49cdb77e5e3c5d37a634bdc482d2146c
Acceso en línea:https://hdl.handle.net/10272/28207
Access Level:acceso abierto
Palabra clave:Catalysts
Copper
Functionalization
Hydrocarbons
Organic reactions
2306.11 Compuestos Organometálicos
2210.01 Catálisis
Descripción
Sumario:The catalytic conversion of CH4 into CH3X compounds has been reported in a few cases, usually involving dehydrogenative processes in which the H atom is lost. Aiming at expanding this limited set of transformations, we have investigated the methane amidation reaction through metal-catalyzed nitrene transfer reactions, a transformation that remains unreported to date for the lightest hydrocarbon. Herein, we describe the use of copper-based catalysts for the direct, nondehydrogenative amidation reaction of methane via a metal-mediated formal nitrene insertion into the C−H bond, a reaction that is also extended to the series of gaseous alkanes. Mechanistic studies, supported by DFT calculations, a microkinetic model, and experimental evidence have led to the proposal of a metallonitrene intermediate responsible for this C−H amidation process via sequential hydrogen abstraction and rebound steps.