Autor segons l'article: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M
Departament: Química Física i Inorgànica
Autor/s de la URV: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar / Saltó De La Torre, Joan
Paraules clau: Palladium Nmr study N-ligands Molecular-orbital methods Modular ligands Mixed p,n-ligands Mixed p Kinetic resolution Force-field parameters Enantioselective allylation Dft calculations Cyclobutane backbone Basis-sets Asymmetric-synthesis Asymmetric allylic substitution Alkylation Ab-initio
Resum: © 2019 American Chemical Society. A method for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)−1) and excellent enantioselectivities (ee's up to 99%) have been achieved for many hindered and unhindered substrates with a wide range of C-, O-, and N-nucleophiles (73 substitution products in total). Moreover, DFT and NMR studies of the key Pd-allyl complexes allowed us to better understand the origin of the excellent enantioselectivities observed experimentally. The useful application of the Pd/phosphite-oxazoline catalysts was demonstrated by the syntheses of many chiral carbobicycles, with multiples stereocenters, by simple sequential reactions involving Pd-allylic substitution and either 1,6-enyne cyclization or Pauson−Khand enyne cyclization.
Àrees temàtiques: Química Materiais Interdisciplinar General chemistry Engenharias ii Ciências agrárias i Chemistry, physical Chemistry (miscellaneous) Chemistry (all) Catalysis Astronomia / física
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 21555435
Adreça de correu electrònic de l'autor: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat joan.salto@estudiants.urv.cat joan.salto@estudiants.urv.cat
Identificador de l'autor: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508 0000-0003-4846-8473 0000-0003-4846-8473
Pàgina final: 6048
Data d'alta del registre: 2023-12-16
Volum de revista: 9
Versió de l'article dipositat: info:eu-repo/semantics/submittedVersion
Enllaç font original: https://pubs.acs.org/doi/10.1021/acscatal.9b01166
URL Document de llicència: http://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Acs Catalysis. 9 (7): 6033-6048
Referència de l'ítem segons les normes APA: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M (2019). An improved class of phosphite-oxazoline ligands for Pd-catalyzed allylic substitution reactions. Acs Catalysis, 9(7), 6033-6048. DOI: 10.1021/acscatal.9b01166
DOI de l'article: 10.1021/acscatal.9b01166
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2019
Pàgina inicial: 6033
Tipus de publicació: Journal Publications
Repositori URV