Author, as appears in the article.: Saltó, J; Tarr, D; Petrov, A; Reich, D; Weber, M; Biosca, M; Pamies, O; Müller, C; Diéguez, M
Department: Química Física i Inorgànica
URV's Author/s: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar
Keywords: Phosphabarrelene Oxazoline-containing ligands Olefins Mechanistic insights Bidentate p,n ligands Asymmetric hydrogenation rh olefins mechanistic insights mechanism evolution cyclic beta-enamides complexes bidentate p,n ligands asymmetric hydrogenation amino-acid-derivatives activation
Abstract: Herein, we report the synthesis of chiral phosphabarrelene-pyridine ligands. Their synthesis benefit from modified reaction conditions to overcome the low yields normally associated with the [4+2] cycloaddition reaction of phosphinines with hexafluoro-2-butyne, which is a key to install the P-stereocenter in the phosphabarrelene. Their potential as chelating ligands in asymmetric catalysis was assessed in the Rh- and Ir-catalyzed hydrogenation of cyclic β-enamides and β-dehydroamino acid derivatives. The catalytic system containing a tert-butyl substituent at the ortho position of the phosphabarrelene moiety successfully hydrogenates a range of cyclic β-enamides (ee's between 92% to 94%) and β-dehydroamino acid derivatives (ee's between 93% to 95%). Moreover, the reactions can be carried out in the environmentally friendly 1,2-propylene carbonate as solvent with no loss of enantioselectivity. Mechanistic studies with the Rh/P,N catalytic systems agree with the Landis-Halpern mechanism and explain the influence of the substituent at the phosphabarrelene on enantioselectivity. Finally, the hydrogenation reactions can be carried out at large scale maintaining high enantioselectivities.
Thematic Areas: Química Organic chemistry Materiais Engenharias iv Engenharias ii Ciências biológicas ii Ciência de alimentos Chemistry, organic Chemistry, applied Catalysis Biodiversidade Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat
Author identifier: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508
Record's date: 2024-05-11
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://onlinelibrary.wiley.com/doi/full/10.1002/adsc.202301358
Papper original source: Advanced Synthesis & Catalysis. 366 (4): 813-821
APA: Saltó, J; Tarr, D; Petrov, A; Reich, D; Weber, M; Biosca, M; Pamies, O; Müller, C; Diéguez, M (2024). Chiral 1-Phosphabarrelene-Pyridines as Suitable Ligands for the Rh/Ir-Catalyzed Asymmetric Hydrogenation of Olefins. Advanced Synthesis & Catalysis, 366(4), 813-821. DOI: 10.1002/adsc.202301358
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1002/adsc.202301358
Entity: Universitat Rovira i Virgili
Journal publication year: 2024
Publication Type: Journal Publications