ESR10 Project

Immobilization of NHC’s ligands in Janus Dendrimers. Catalysis in green solvents

Recruting institution: UW
Diploma-delivering institutions: UW, UAB
Thesis co-directors:
Karol Grela (UW, Warsaw, PL), Rosa Maria Sebastián (UAB, Barcelona, ES)
Secondment host: Henkel KGaA (ES)
Academic secondment: LCC (Toulouse, France)

Objectives
To prepare phosphorus Janus dendrimers[1] as support for NHC-based catalysts for metathesis reactions in different media.[2,3] The incorporation of polyoxyethylenated chains in the macromolecules will provide water solubility, and polyfluorinated chains will allow catalysis in supercritical CO2, enabling the catalysis to be performed in green solvents.[4] Several generations of dendrimers will be prepared and the dendritic effect on the activity and selectivity of catalytic moieties will be analyzed.
Expected Results
At least 10 new families of Janus dendrimers (monodisperse polymers) will be obtained, of 3 different generations for each, combining at least 5 newly obtained NHCs, and moieties that will allow their solubility to be modulated mainly in green solvents (water and CO2). Positive dendritic effect are expected when working with different generations. The recovering and reuse of the new macromolecular catalysts at the minimum 10-20 catalytic cycles will improve the TON and TOF in comparison to parental complexes.

[1] A. M. Caminade, C. O. Turrin, R. Laurent, A. Ouali, B. Delavaux-Nicot in Dendrimers: Towards Catalytic, Material and Biomedical Uses, Wiley-VCH, Chistester, 2011.
[2] K. Skowerski, J. Białecki, S. J. Czarnocki, K. Żukowska, K. Grela; Beilstein J. Org. Chem. 2016, 12, 5–15.
[3] G. Szczepaniak, K. Kosiński, K. Grela Green Chem.2014, 16, 4474-4492.
[4] Y. Feng, Y.-M. He, L.-W. Zhao, Y.-Y. Huang, Q.-H. Fan Org. Lett., 2007, 9, 2261–2264.