Author, as appears in the article.: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M
Department: Química Física i Inorgànica
URV's Author/s: Besora Bonet, Maria / BORRÀS NOGUERA, CARLOTA / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pastor Gosálbez, María Inmaculada
Keywords: 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
Abstract: 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%).
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat inma.pastor@urv.cat
Author identifier: 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656 0000-0003-4913-0722
Record's date: 2024-07-27
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.acs.org/doi/10.1021/acs.organomet.1c00450
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Organometallics. 40 (20): 3424-3435
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
Article's DOI: 10.1021/acs.organomet.1c00450
Entity: Universitat Rovira i Virgili
Journal publication year: 2021
Publication Type: Journal Publications