Fitting the catalysts for effective enantioselective C-X bond forming reactions. Theoretically guided ligand design and mechanistic investigations

Identificador:  TDX:2887

Handle: https://hdl.handle.net/20.500.11797/TDX2887

Autores:  Biosca Brull, Maria

Resumen:
The growing demand on enantiomerically pure compounds has stimulated the interest for the development of methodologies to obtain these compounds. Among them, asymmetric catalysis is one of the most employed tools. In this technic, the choice of the chiral ligand is fundamental to obtain high levels of activity and enantioselectivity. In this context, this thesis is focused on the synthesis of several families of highly modular chiral ligands from readily available starting materials. Particularly, we worked on the synthesis of P-oxazoline (P= phosphine, phosphinite, phosphite, phosphoroamidite), P-other N-donor groups (P= phosphite, phosphoroamidite, phosphonite and N= thiazole, sulfoximine, hydrazone, amine, pyridine), P-thioether (P= phosphine, phosphinite, phosphite) and a family of P*-stereogenic phosphine-phosphite ligands. These ligands have been applied in the Rh- and Ir-catalyzed hydrogenation of functionalized and minimally functionalized olefins, Pd-catalyzed allylic substitution reaction and Pd-catalyzed decarboxylative protonation. Furthermore, in some cases, DFT studies in combination with experimental ones have been performed to better understand the origin of the obtained enantioselectivities or in order to guide the ligand optimization.