Martínez Laguna, JonathanCholewinska, AnnaBorrego, ElenaBesora, MaríaÁlvarez, MaríaCaballero Bevia, AnaPérez Romero, Pedro José2026-04-212026-04-212026Martínez-Laguna, J., Cholewinska, A., Borrego, E., Besora, M., Álvarez, M., Caballero, A., & Pérez, P. J. (2026). Methane Catalytic Amidation via a Plausible Copper-Nitrene Intermediate. Journal of the American Chemical Society, 148(8), 9057–9065. https://doi.org/10.1021/jacs.5c227470002-78631520-5126 (electrónico)https://hdl.handle.net/10272/28207The 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.engAttribution 4.0 Internationalhttp://creativecommons.org/licenses/by/4.0/CatalystsCopperFunctionalizationHydrocarbonsOrganic reactionsjournal article10.1021/jacs.5c22747open access2306.11 Compuestos Organometálicos2210.01 Catálisis