Author, as appears in the article.: Cruz-Sánchez PDL; Faiges J; Mazloomi Z; Borràs C; Biosca M; Pàmies O; Diéguez M
Department: Química Física i Inorgànica Química Física i Inorgànica
URV's Author/s: Biosca Brull, Maria / BORRÀS NOGUERA, CARLOTA / De La Cruz Sánchez Badia, Pol / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar
Keywords: 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
Abstract: © 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.
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
ISSN: 02767333
Author's mail: maria.biosca@urv.cat pol.delacruzsanchez@estudiants.urv.cat pol.delacruzsanchez@estudiants.urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat
Author identifier: 0000-0002-9116-6318 0000-0002-2352-8508 0000-0002-8450-0656
Last page: 4205
Record's date: 2024-07-13
Journal volume: 38
Papper version: info:eu-repo/semantics/acceptedVersion
Papper original source: Organometallics. 38 (21): 4193-4205
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
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1021/acs.organomet.9b00514
Entity: Universitat Rovira i Virgili
Journal publication year: 2019
First page: 4193
Publication Type: Journal Publications