Autor segons l'article: Montserrat Diéguez; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; Oscar Pàmies
Departament: Química Física i Inorgànica
Autor/s de la URV: DIÉGUEZ FERNÁNDEZ, MONTSERRAT; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; PAMIES OLLÉ, OSCAR
Paraules clau: rhodium hydroxyamide ligands asymmetric transfer hydrogenation
Resum: 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.
Grup de recerca: Organometàl.lics i Catàlisi Homogènia
Àrees temàtiques: Chemistry Química Química
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 1615-4169
Identificador de l'autor: 0000-0002-8450-0656; n/a; 0000-0003-2013-8093; 0000-0003-1271-4601; n/a; 0000-0002-2352-8508
Data d'alta del registre: 2017-01-18
Pàgina final: 4018
Volum de revista: 358
Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
Enllaç font original: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201600903
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI de l'article: 10.1002/adsc.201600903
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2016
Pàgina inicial: 4006
Tipus de publicació: Post-print
Repositori URV