Autor según el artículo: Maria Biosca; Marc Magre; Per-Ola Norrby; Oscar Pàmies; Montserrat Diéguez

Departamento: Química Física i Inorgànica

Autor/es de la URV: BIOSCA BRULL, MARIA; Marc Magre; Per-Ola Norrby; PAMIES OLLÉ, OSCAR; DIÉGUEZ FERNÁNDEZ, MONTSERRAT

Palabras clave: DFT calculations allylic substitution palladium

Resumen: 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.

Grupo de investigación: Organometàl.lics i Catàlisi Homogènia

Áreas temáticas: Chemistry Química Química

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 1867-3880

Identificador del autor: n/a; n/a; 0000-0002-2419-0705; 0000-0002-2352-8508; 0000-0002-8450-0656

Fecha de alta del registro: 2017-02-22

Página final: 4107

Volumen de revista: 7

Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion

Enlace a la fuente original: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/cctc.201500873

DOI del artículo: 10.1002/cctc.201500873

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2015

Página inicial: 4091

Tipo de publicación: Post-print