Oxidovanadium(IV) sulfate catalyses light-driven C-N bond formation
Gaspa, Silvia (Università di Sassari. Dipartimento di Scienze Chimiche)
Sciortino, Giuseppe (Institut d'Investigacions Químiques de Catalunya)
Porcheddu, Andrea (Università degli Studi di Cagliari)
Dell'Osa, Chiara (Università di Sassari. Dipartimento di Scienze Chimiche)
Satta, Giuseppe (Università di Sassari. Dipartimento di Scienze Chimiche)
Azzena, Ugo (Università di Sassari. Dipartimento di Scienze Chimiche)
Pisano, Luisa (Università di Sassari. Dipartimento di Scienze Chimiche)
Carraro, Massimo (Università di Sassari. Dipartimento di Scienze Chimiche)
Sanna, Daniele (Istituto CNR di Chimica Biomolecolare)
Garribba, Eugenio (Università di Sassari. Dipartimento di Medicina, Chirurgia e Farmacia)
Maseras Cuní, Feliu (Institut d'Investigacions Químiques de Catalunya)
De Luca, Lidia (Università di Sassari. Dipartimento di Scienze Chimiche)

Data:	2023
Resum:	Oxidovanadium(IV) sulfate, VIVOSO4, is shown to catalyze efficiently the amidation of the C-H bond of aldehydes by N-chloramine derivatives for the selective synthesis of amides. The catalytic process is driven by visible light irradiation at room temperature, and the reaction is carried out in ethyl acetate, a green and bio-based solvent. The catalyst, as an inorganic salt of an earth-abundant transition metal, is easily available, stable and inexpensive and is superior compared to other tested transition metal salts and complexes. The proposed reaction mechanism is obtained through the use of a combination of experimental and computational techniques. EPR spectroscopy suggests an interaction of the amine with the VIVO2+ ion and the formation of VIV/VV and radical organic intermediates. Density functional theory (DFT) unveils a light-induced radical mechanism via an unusual VIVOCl(SO4) complex. The mechanistic proposal opens perspectives for the extended application of vanadium salts toward highly desirable dechlorination processes as well as for harsh C-H activations.
Ajuts:	Agencia Estatal de Investigación PID2020-112825RB-I00 Ministerio de Ciencia e Innovación CEX2019-000925-S Ministerio de Ciencia e Innovación FJC2019-039135-I
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, i la comunicació pública de l'obra, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original. No es permet la creació d'obres derivades.
Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Matèria:	Aldehydes ; C-N bond formation ; DFT Mechanism ; N-chloramine ; Oxidovanadium(IV) sulfate ; Photocatalysis
Publicat a:	Molecular Catalysis, Vol. 541 (April 2023) , art. 113054, ISSN 2468-8231

DOI: 10.1016/j.mcat.2023.113054

Disponible a partir de: 2025-04-30 Postprint

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