Ligand design for palladium and iridium selective catalysts

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)

 

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