- Supramolecular orientation of substrates in the transition metal catalyzed asymmetric hydrogenation reaction
- Award date
- 19 February 2016
- Number of pages
- Document type
- PhD thesis
- Faculty of Science (FNWI)
- Van 't Hoff Institute for Molecular Sciences (HIMS)
This thesis describes a detailed study of a catalytic system in which hydrogen bonds are formed between two ligand building blocks as well as between the catalyst and the substrate during the asymmetric hydrogenation reaction catalyzed by rhodium complexes. The understanding of the mechanism involved in this transformation allowed us to design a second generation of catalyst that showed higher activity in the hydrogenation of functionalized substrates while excellent selectivity is maintained. Also, the same supramolecular strategy was applied for the formation of iridium complexes.
The work described in this thesis gives detailed insights in how hydrogen bonds can be involved in the asymmetric hydrogenation reaction catalyzed by supramolecular rhodium complexes. The design of a traditional catalyst and its optimization is based on the modification of electronic and steric parameters that can be changed in the structure of the catalyst. The results stemming from the current study show that hydrogen bonds between the catalyst and the substrate can be an important factor to induce high rates of reactions and high selectivities. It remains to be seen if this concept can be used for other reactions.
- Research conducted at: Universiteit van Amsterdam
Thesis (complete) (Embargo until 19 February 2018)
Chapter 2: Origin of the selectivity and activity in the Rhodium-catalyzed asymmetric hydrogenation using supramolecular ligands (Embargo until 19 February 2018)
Chapter 3: Computational modeling of the supramolecular Rhodium-catalyzed asymmetric hydrogenation: Reaction pathways and origin of enantioselection (Embargo until 19 February 2018)
Chapter 4: Phosphine oxide based supramolecular ligands in the Rhodium-catalyzed asymmetric hydrogenation (Embargo until 19 February 2018)
Chapter 5: Supramolecular Iridium complexes in asymmetric hydrogenation (Embargo until 19 February 2018)
- Supplementary materials
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