Autor segons l'article: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M
Departament: Química Física i Inorgànica
Autor/s de la URV: Besora Bonet, Maria / BORRÀS NOGUERA, CARLOTA / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pastor Gosálbez, María Inmaculada
Paraules clau: Iridium-catalyzed hydrogenation selective catalysts phosphite-oxazoline ligands molecular-orbital methods mechanistic insights highly enantioselective hydrogenation gaussian-type basis effective core potentials cyclic beta-enamides basis-sets
Resum: In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%).
Àrees temàtiques: 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
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat inma.pastor@urv.cat
Identificador de l'autor: 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656 0000-0003-4913-0722
Data d'alta del registre: 2024-07-27
Versió de l'article dipositat: info:eu-repo/semantics/publishedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.organomet.1c00450
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Organometallics. 40 (20): 3424-3435
Referència de l'ítem segons les normes APA: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M (2021). Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins. Organometallics, 40(20), 3424-3435. DOI: 10.1021/acs.organomet.1c00450
DOI de l'article: 10.1021/acs.organomet.1c00450
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2021
Tipus de publicació: Journal Publications