EffectiveN-methylation of nitroarenes with methanol catalyzed by a functionalized NHC-based iridium catalyst: a green approach toN-methyl amines

González-Lainez, Miguel ; Jiménez, M. Victoria (Universidad de Zaragoza) ; Passarelli, Vicenzo (Universidad de Zaragoza) ; Pérez-Torrente, Jesús J. (Universidad de Zaragoza)

Resumen: Compound [IrBr(CO)2(¿C-tBuImCH2PyCH2OMe)] featuring a flexible pyridine/OMe functionalized NHC ligand ¿1C coordinated efficiently catalyzes the selective N-monomethylation of nitroarenes using methanol as both the reducing agent and the C1 source. A range of functionalized nitroarenes including heterocyclic or sterically hindered derivatives have been efficiently converted to the corresponding N-monomethyl amines in good yields at low catalyst loadings using sub-stoichiometric amounts of Cs2CO3 as a base. Mechanistic investigations support a borrowing-hydrogen mechanism in which methanol acts as the hydrogen source and methylating agent. Further, the hydrogen transfer reduction of nitrobenzene to aniline under optimized reaction conditions should proceed through a direct mechanism involving nitrosobenzene and N-phenylhydroxylamine intermediates.

Idioma: Inglés

DOI: 10.1039/d0cy00707b

Año: 2020

Publicado en: Catalysis Science and Technology 10, 10 (2020), 3458-3467
ISSN: 2044-4753

Factor impacto JCR: 6.119 (2020)

Categ. JCR: CHEMISTRY, PHYSICAL rank: 44 / 162 = 0.272 (2020) - Q2 - T1

Factor impacto SCIMAGO: 1.635 - Catalysis (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/Building Europe from Aragon
Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E42-17R
Financiación: info:eu-repo/grantAgreement/ES/MICINN-FEDER/CTQ2016-75884-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO/BES-2014-069624

Tipo y forma: Artículo (PostPrint)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)