Asymmetric metal- and organocatalysis in organic synthesis
Title: "Asymmetric metal- and organocatalysis in organic synthesis"
Main researcher: Carmen Nájera Domingo
Type: R & D Project
Start Date: 01/01/2011
End date: 31/12/2013 (extended until 31/12/2014)
Total awarded: 335,170.00 €
Funding organization: Spanish Ministry of Science and Innovation (MICCIN) with funds from the State Budget (PGE)
The presented proposal deals with the preparation and study of the activity and selectivity of chiral metallic catalysts and chiral organocatalysts in different asymmetric reactions, paying special attention to the recyclability and reuse of the catalysts with the aim of using them in large-scale processes and continous-flow reactors.
Regarding the asymmetric synthesis studies employing chiral metallic catalysts, firstly, we will synthesize chiral palladium complexes, derived from oxime palladacycles and other more traditional palladium sources, by reaction with different chiral ligands, in order to apply them in enantioselective Suzuki-Miyaura cross-coupling reactions involving boron complexes and aryl-, allyl, and benzyl electrophiles. On the other hand, we will also study the activity of newly prepared gold(I) and silver(I) chiral catalysts in asymmetric two- and three-component 1,3-dipolar cycloadditions involving azomethine ylides, as well as in the inter- and intramolecular asymmetric hydroamination reaction of alkenes and dienes.
With respect to the asymmetric organocatalysis, we want to perform the synthesis of new and recyclable chiral 2-aminobenzimidazole-derived organocatalysts in order to study their reactivity and selectivity in asymmetric conjugate additions involving heteronucleophiles, and in different bi- and multicomponent processes with the aim of preparing highly functionalized chiral carbo- and heterocycles. On the other hand, we will synthesized and use recyclable dimeric chiral ammonium salts derived from Cinchona alkaloids as phase transfer organocatalysts in enantioselective a-functionalization reactions (alkylations and aminations) of b-ketoesters and 3-substituted 2-oxoindole derivatives. Finally, we pretend to immobilize in different polymeric materials chiral bifunctional BINAM/proline-derived organocatalysts planning to study their activity and selectivity in enantioselective C-C and C-heteroatom bond forming processes such as, the aldol, Mannich, Michael, and a-functionalization of carbonyl compounds reactions.
Department of Organic Chemistry
Universidad de Alicante Facultad de Ciencias, Fase I Carretera de San Vicente del Raspeig S/N 03690 San Vicente del Raspeig Alicante (Spain)