Tesis doctoral de Verónica De La Fuente Molina
This doctoral thesis focuses on the synthesis of new ligands and their application in two types of catalytic process: a) palladium catalysed carbonylation reactions and b) asymmetric reactions (hydrogenation of challenge substrates and c-c bond formation). In the first part of the thesis, the synthesis of a family of new diphosphine ligands and their application in pd-catalysed carbonylation processes is described. These ligands were first used in the pd-catalysed methoxycarbonylation of [+]ethane, achieving high activity and selectivity. A mechanistic study on these catalytic systems revealed the resting state of this process. The new ligands were also applied in the aminocarbonylation and double-carbonylation of aryl iodides, achieving high level of chemoselectivity in each case. Nmr studies on these systems led to the discovery and development of the first phosphine-free pd-catalysed double-carbonylation of aryl iodides where the base used in the process revealed to also play a key role as ligand and nucleophile. The second part of this thesis describes the synthesis of new phosphino-imidazoline ligands and their application in the ir-catalysed asymmetric hydrogenation of unfunctionalised olefines and imines achieving moderate enantioselectivities. These ligands were also applied in the pd-catalysed allylic substitution reactions, achieving excellent enantioselectivities for a wide range of substrates and nucleophiles. An efficient recovery of the catalytic system was carried out by anchoring a phosphino-imidazoline ligand onto a polymer support or using ionic liquids as reaction medium. [-]
Datos académicos de la tesis doctoral «Ligand design for palladium and iridium selective catalysts«
- Título de la tesis: Ligand design for palladium and iridium selective catalysts
- Autor: Verónica De La Fuente Molina
- Universidad: Rovira i virgili
- Fecha de lectura de la tesis: 13/05/2011
Dirección y tribunal
- Director de la tesis
- Carmen Claver Cabrero
- Tribunal
- Presidente del tribunal: ernesto Carmona guzmán
- jonathan a. Iggo (vocal)
- Miguel ángel Pericí s brondo (vocal)
- johannes g. De vries (vocal)