Autor según el artículo: Cruz-Sánchez PDL; Faiges J; Mazloomi Z; Borràs C; Biosca M; Pàmies O; Diéguez M

Departamento: Química Física i Inorgànica Química Física i Inorgànica

Autor/es de la URV: Biosca Brull, Maria / BORRÀS NOGUERA, CARLOTA / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar

Palabras clave: Selective catalysts Oxazoline ligands N-heterocyclic carbenes Molecular-orbital methods Mixed phosphorus/sulfur ligands Minimally functionalized olefins Iridium-catalyzed hydrogenation Imidazolium salts Basis-sets Ab-initio

Resumen: © 2019 American Chemical Society. We studied for the first time the potential of novel and simple Ir/thioether-NHC complexes in the asymmetric hydrogenation of unfunctionalized olefins and cyclic β-enamides. For comparison, we prepared and applied the analogues thioether-phosphinite/phosphite complexes. We found that the efficiency of the new Ir/thioether-NHC catalyst precursors varies with the type of olefin. Thus, while the Ir/thioether-NHC catalyst precursors provided lower catalytic performance than their related Ir/thioether-P complexes in the hydrogenation of olefins lacking a coordinating group, the catalysts had similar good performance for the reduction of functionalized olefins (e.g., tri- and disubstituted enol phosphonate derivatives). Catalytic results together with the studies of the reactivity toward H2 indicated that the thioether-carbene design favors the formation of inactive trinuclear species, which are responsible for the low activities obtained with these carbene-type catalysts. Nevertheless, this catalyst deactivation can be avoided by using functionalized olefins such as enol phosphonates. We also report the discovery of simple-to-synthesize Ir/thioether-P catalysts containing a simple backbone that gave high enantioselectivities for some trisubstituted olefins, some challenging 1,1′-disubstituted olefins, and cyclic β-enamides.

Áreas temáticas: Química Physical and theoretical chemistry Organic chemistry Materiais Inorganic chemistry Engenharias ii Ciências biológicas ii Ciências agrárias i Chemistry, organic Chemistry, inorganic & nuclear Astronomia / física

ISSN: 02767333

Direcció de correo del autor: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat

Identificador del autor: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508

Página final: 4205

Fecha de alta del registro: 2023-02-22

Volumen de revista: 38

Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion

URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/

Referencia al articulo segun fuente origial: Organometallics. 38 (21): 4193-4205

Referencia de l'ítem segons les normes APA: Cruz-Sánchez PDL; Faiges J; Mazloomi Z; Borràs C; Biosca M; Pàmies O; Diéguez M (2019). Ir/Thioether-Carbene, -Phosphinite, and -Phosphite Complexes for Asymmetric Hydrogenation. A Case for Comparison. Organometallics, 38(21), 4193-4205. DOI: 10.1021/acs.organomet.9b00514

DOI del artículo: 10.1021/acs.organomet.9b00514

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2019

Página inicial: 4193

Tipo de publicación: Journal Publications