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Leitlinien Unfallchirurgie
5. Auflage bestellen |
Indice, Datei (54 KB)
Lectura de prueba, Datei (410 KB)
ISBN-10 (Impresion) | 3954040417 |
ISBN-13 (Impresion) | 9783954040414 |
ISBN-13 (E-Book) | 9783736940413 |
Idioma | Inglés |
Numero de paginas | 262 |
Laminacion de la cubierta | Brillante |
Edicion | 1 Aufl. |
Volumen | 0 |
Lugar de publicacion | Göttingen |
Lugar de la disertacion | Basel |
Fecha de publicacion | 05.03.2012 |
Clasificacion simple | Tesis doctoral |
Area |
Química
|
This work was dedicated to the development and evaluation of new chiral catalysts for asymmetric C-C and C-H bond forming reactions.
In the first part of the thesis an ESI-MS screening method is described, which allows the determination of a chiral catalyst´s selectivity in the palladium catalyzed asymmetric allylic alkylation by testing its racemic form. The value of this new method was demonstrated when different new aryl-PHOX-type ligands, which are not easily accessible in their enantiopure form, were evaluated.
In the second part new PHOX-type ligands were tested in the iridium-catalyzed asymmetric hydrogenation of different unsaturated compounds. Although low activities and selectivities were found in most cases, one ligand showed promising results in the hydrogenation of allylic alcohols and imines.
Furthermore air- and moisture-stable secondary phosphine oxide (SPO) containing bidentate ligands were tested in the palladium-catalyzed asymmetric allylic alkylation reaction. SPO,N-ligands bearing a PHOX type backbone were inactive in this transformation as they tend to form inactive palladium-bis-ligand complexes. SPO,P ligands however, were able to promote the desired reaction in a highly selective fashion although only low activities were found.
During this work as well a new organo-catalyst, based on the structure of 2,3-dihydrobenzo[1,4]oxazine, was developed which allows for the asymmetric organo-catalyzed transfer-hydrogenation of α,β-unsaturated aldehydes. This catalyst was able to reduce for the first time β, β-diaryl acrylaldehydes with very good activities and high enantioselectivities.
Moreover an ESI-MS based mechanistic study on the tripeptide catalyzed conjugate addition reaction of aldehydes to nitroolefins was carried out. By this all reaction intermediates postulated for an enamine mechanism have been detected. Furthermore the attack of the enamine onto the nitroolefin was found to be the selectivity determining step in this process.
The last part of this work aimed for the asymmetric α -allylation of carbonyl compounds by a tandem-catalysis approach. An intensive screening of both the organo-catalyst and the palladium-ligand led to reaction conditions which allowed for the selective mono-allylation of ketones in high yields. The formation of a quaternary center by α -allylation of α -branched aldehydes was also achieved. However, only low enantiomeric excesses were obtained in this transformation for the different catalyst systems tested.