Repositori institucional URV
| 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 |
| Author, as appears in the article.: | de la Cruz-Sanchez, Pol; Faiges, Jorge; Mazloomi, Zahra; Borras, Carlota; Biosca, Maria; Pamies, Oscar; Dieguez, Montserrat |
| Author's mail: | maria.biosca@urv.cat jorge.faiges@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 |
| Journal publication year: | 2019 |
| Publication Type: | Journal Publications |
| ISSN: | 02767333 |
| APA: | de la Cruz-Sanchez, Pol; Faiges, Jorge; Mazloomi, Zahra; Borras, Carlota; Biosca, Maria; Pamies, Oscar; Dieguez, Montserrat (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 |
| Paper original source: | Organometallics. 38 (21): 4193-4205 |
| 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. |
| Article's DOI: | 10.1021/acs.organomet.9b00514 |
| Paper version: | info:eu-repo/semantics/acceptedVersion |
| Department: | Química Física i Inorgànica Química Física i Inorgànica |
| Licence document URL: | https://repositori.urv.cat/ca/proteccio-de-dades/ |
| 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 |
| 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 |
| Entity: | Universitat Rovira i Virgili |
| Record's date: | 2025-01-27 |
| First page: | 4193 |
| Last page: | 4205 |
| Journal volume: | 38 |
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