Author, as appears in the article.: Maria Biosca; Marc Magre; Per-Ola Norrby; Oscar Pàmies; Montserrat Diéguez

Department: Química Física i Inorgànica

URV's Author/s: BIOSCA BRULL, MARIA; Marc Magre; Per-Ola Norrby; PAMIES OLLÉ, OSCAR; DIÉGUEZ FERNÁNDEZ, MONTSERRAT

Keywords: DFT calculations allylic substitution palladium

Abstract: A new library of modular amino phosphite ligands obtained in a few synthetic steps from enantiopure amino alcohols has been tested in asymmetric Pd-catalyzed allylic substitution. The modular ligand design is crucial to find highly selective catalysts for each substrate type using a wide range of C-, N-, and O-nucleophiles. A DFT study of the species responsible for the enantiocontrol was used to optimize the ligand structure. By selecting the ligand components, we were able to identify unprecedented catalytic systems that can create new chiral C-C, C-N, and C-O bonds in a variety of substrate types (hindered and unhindered) in high yields and enantioselectivities (ee values up to 99 %). Further studies on the Pd-π-allyl intermediates provided a deep understanding of the effect of ligand structure in the origin of enantioselectivity. Potential applications of the new Pd/amino phosphite catalysts were demonstrated by the practical synthesis of a range of chiral carbocycles by simple tandem reactions, with no loss of enantioselectivity.

Research group: Organometàl.lics i Catàlisi Homogènia

Thematic Areas: Chemistry Química Química

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

ISSN: 1867-3880

Author identifier: n/a; n/a; 0000-0002-2419-0705; 0000-0002-2352-8508; 0000-0002-8450-0656

Record's date: 2017-02-22

Last page: 4107

Journal volume: 7

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

Link to the original source: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cctc.201500873

Article's DOI: 10.1002/cctc.201500873

Entity: Universitat Rovira i Virgili

Journal publication year: 2015

First page: 4091

Publication Type: Post-print