Author, as appears in the article.: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M

Department: Química Física i Inorgànica

URV's Author/s: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar

Keywords: 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

Abstract: © 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.

Thematic Areas: Química Materiais Interdisciplinar General chemistry Engenharias ii Ciências agrárias i Chemistry, physical Chemistry (miscellaneous) Chemistry (all) Catalysis Astronomia / física

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 21555435

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

Last page: 6048

Record's date: 2023-02-22

Journal volume: 9

Papper version: info:eu-repo/semantics/submittedVersion

Link to the original source: https://pubs.acs.org/doi/10.1021/acscatal.9b01166

Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/

Papper original source: Acs Catalysis. 9 (7): 6033-6048

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

Article's DOI: 10.1021/acscatal.9b01166

Entity: Universitat Rovira i Virgili

Journal publication year: 2019

First page: 6033

Publication Type: Journal Publications