Author, as appears in the article.: Mazloomi Z; Magre M; Del Valle E; Pericàs MA; Pàmies O; van Leeuwen PWNM; Diéguez M

Department: Química Física i Inorgànica

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

Keywords: Palladium P,n-ligands Kinetic study Intermolecular heck reaction Asymmetric catalysis

Abstract: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim This study identifies new phosphite-oxazoline ligands that have been successfully applied in the palladium-catalyzed intermolecular asymmetric Heck reaction. The design of the new phosphite-oxazoline ligands derives from a previous successful generation of phosphine-oxazoline ligands, by replacing the phosphine group with several π-acceptor biaryl phosphite moieties. With these simple modifications, the new phosphite-based ligands, unlike previous phosphine-oxazoline, not only present a modular design with numerous potential phosphite groups available, but they are also air-stable solids, which can be made in the same number of synthetic steps as the phosphine analogues. The substitution of the phosphine by a biaryl phosphite group extended the range of substrates and triflates sources that can be coupled with regio-, enantioselectivities and activities comparable to the few best ones reported. In addition, the ligands that provided the best selectivities contained an isopropyl oxazoline moiety instead of the tert-butyl group found in the related phosphine-oxazoline ligands, which is made from a much more expensive precursor. In this paper we have also carried out kinetic studies and a Hammett plot analysis to determine the rate determining step of this system in the regime of interest. We suggest a likely explanation for the fast Heck reaction of the phosphite-oxazoline catalysts. (Figure presented.).

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/

ISSN: 1615-4150

Author's mail: montserrat.dieguez@urv.cat oscar.pamies@urv.cat

Author identifier: 0000-0002-8450-0656 0000-0002-2352-8508

Record's date: 2023-02-18

Journal volume: 360

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

Link to the original source: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201701603

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

Papper original source: Advanced Synthesis & Catalysis. 360 (8): 1650-1664

APA: Mazloomi Z; Magre M; Del Valle E; Pericàs MA; Pàmies O; van Leeuwen PWNM; Diéguez M (2018). Synthesis, Application and Kinetic Studies of Chiral Phosphite-Oxazoline Palladium Complexes as Active and Selective Catalysts in Intermolecular Heck Reactions. Advanced Synthesis & Catalysis, 360(8), 1650-1664. DOI: 10.1002/adsc.201701603

Article's DOI: 10.1002/adsc.201701603

Entity: Universitat Rovira i Virgili

Journal publication year: 2018

Publication Type: Journal Publications