ESR8 Project

Polar substrates asymmetric hydrogenation and associated processes: role of the base

Recruting institution: UoY
Diploma-delivering institutions: UoY, UPS
Thesis co-directors: Simon Duckett; Jason Lynam and John Slattery (UoY, York, UK), Rinaldo Poli (LCC, Toulouse, FR)
Secondment host: Fundacion Tecnalia Research & Innovation (ES)
Academic secondment : UAB (Barcelona, ES)

Objectives
In hydrogenation and transfer hydrogenation of polar substrates, new mechanistic views have recently emerged to account for the activity of system with non-deprotonatable ligands, which nevertheless need a strong base for activity.[1] Through a combination of ligand synthesis, catalysis and mechanistic studies by advanced NMR and DFT calculations, this project targets mechanistic understanding and the development of predictive tools for optimizing the ligand structure, given specific prochiral substrates of industrial interest.
Expected Results
Clarification of the operating cycle for the asymmetric hydrogenation and transfer hydrogenation with Rh and Ir systems. Design of ligands able to maximize activity and enantioselectivity for target substrates. At least one catalytic system with TOF > 500 h-1 at 25°C and e.e. > 95% for a model substrate of the acetophenone family.

[1] (a) Dub, P. A.; Henson, N. J.; Martin, R. L.; Gordon, J. C. J. Am. Chem. Soc. 2014, 136, 3505. (b) Hayes, J. M.; Deydier, E.; Ujaque, G.; Lledós, A.; Malacea, R.; Manoury, E.; Vincendeau, S.; Poli, R. ACS Catal.2015, 5, 4368.