Autor según el artículo: Montserrat Diéguez; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; Oscar Pàmies
Departamento: Química Física i Inorgànica
Autor/es de la URV: DIÉGUEZ FERNÁNDEZ, MONTSERRAT; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; PAMIES OLLÉ, OSCAR
Palabras clave: rhodium hydroxyamide ligands asymmetric transfer hydrogenation
Resumen: A modular ligand library of α-amino acid hydroxyamides and thioamides was prepared from 10 different N-tert-butyloxycarbonyl-protected α-amino acids and three different amino alcohols derived from 2,3-O-isopropylidene-α-d-mannofuranoside. The ligand library was evaluated in the half-sandwich ruthenium- and rhodium-catalyzed asymmetric transfer hydrogenation of a wide array of ketone substrates, including simple as well as sterically demanding aryl alkyl ketones, aryl fluoroalkyl ketones, heteroaromatic alkyl ketones, aliphatic, conjugated and propargylic ketones. Under the optimized reaction conditions, secondary alcohols were obtained in high yields and in enantioselectivities up to >99%. The choice of ligand/catalyst allowed for the generation of both enantiomers of the secondary alcohols, where the ruthenium-hydroxyamide and the rhodium-thioamide catalysts act complementarily towards each other. The catalytic systems were also evaluated in the tandem isomerization/asymmetric transfer hydrogenation of racemic allylic alcohols to yield enantiomerically enriched saturated secondary alcohols in up to 98% ee. Furthermore, the catalytic tandem α-alkylation/asymmetric transfer hydrogenation of acetophenones and 3-acetylpyridine with primary alcohols as alkylating and reducing agents was studied. Secondary alcohols containing an elongated alkyl chain were obtained in up to 92% ee.
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: 1615-4169
Identificador del autor: 0000-0002-8450-0656; n/a; 0000-0003-2013-8093; 0000-0003-1271-4601; n/a; 0000-0002-2352-8508
Fecha de alta del registro: 2017-01-18
Página final: 4018
Volumen de revista: 358
Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
Enlace a la fuente original: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201600903
URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI del artículo: 10.1002/adsc.201600903
Entidad: Universitat Rovira i Virgili
Año de publicación de la revista: 2016
Página inicial: 4006
Tipo de publicación: Post-print
Repositori URV