Síntesi de nous lligands P-estereogènics. Aplicacions a la reacció de Pauson-Khand i a la hidrogenació asimètriques
- Autores: Sílvia Orgué Gassol
- Directores de la Tesis: Xavier Verdaguer i Espaulella (dir. tes.)
- Lectura: En la Universitat de Barcelona ( España ) en 2015
- Idioma: catalán
- Tribunal Calificador de la Tesis: Fernando Lopez-Ortiz (presid.), Ciril Jimeno Mollet (secret.), Montserrat Diéguez Fernández (voc.)
- Materias:
- Enlaces
- Tesis en acceso abierto en: Dipòsit Digital de la UB TDX
- Resumen
Phosphorus compounds have demonstrated unique properties as ligands for asymmetric catalysis. Our group has been devoted to the synthesis of P-stereogenic ligands in the last 5 years. The present doctoral thesis is devoted to the design and synthesis of new P-stereogenic ligands and its application in asymmetric catalysis. We synthesized a new family of P-stereogenic diphosphines called ThaxPHOS. These ligands were complexed to cobalt and the resulting catalysts have been studied for the catalytic and asymmetric Pauson-Khand reaction between norbornadiene and different terminal alkynes. As a result of this study the corresponding enones were obtained with unprecedented results so far. Next, we have developed a versatile method for the synthesis of new P-stereogenic ligands from optically pure aminophosphines. The acidic hydrolisis of aminophosphines was performed giving rise to phosphinous acid boranes. This compounds were used as electrophiles for nucleophilic substitutions at the P centre. Using this methodology it was synthesized a new family of P estereogenic ligands. In order to show the usefulness of the new methodology developed, it was synthesized a new family of phosphino-oxazoline ligands, which have been used for iridium catalysed asymmetric hydrogenation. The catalysts obtained showed high activity for this type of reaction, giving rise to the hydrogenated products with high selectivity in some cases.
