Supramolecular orientation of substrates in the transition metal catalyzed asymmetric hydrogenation reaction

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.