DEVELOPMENT OF CHIRAL LIGANDS FROM NATURAL MOLECULES FOR METAL-PROMOTED ASYMMETRIC CATALYSIS

The main aim of this PhD thesis was the development of a new family of chiral ligands derived from D-glucose (elpaN-type). These ligands were designed in order to be pseudo-enantiomeric respect to the previously developed Naple-type family, and focusing on the obtainment of easy and straightforward synthesis. On this basis, three libraries of elapN-type ligands were prepared and successfully employed in homogenous metal-promoted asymmetric catalysis: the elpaN-phos, for the Pd-promoted Asymmetric Allylic Substitution; the elpaN-py, for the Mo-promoted Asymmetric Allylic Alkylation enhanced by microwaves; the elpaN-Salen, for the Mn-promoted Asymmetric Epoxidation. In all cases, performances were excellent and inversion of selectivity respect to the Naple-type family was achieved. In the particular case of the elpaN-phos subset, a phase-tagged version of the ligand was successfully employed in multiphase catalysis, achieving the recycle of the catalyst. The secondary aim of this PhD thesis was the development of a library of sugar-derived, water soluble Pd0 complexes for aqueous Suzuki-Miyaura cross-coupling. Also in this case, good performances were obtained (TOF up to 9500 h-1), among the best in literature for this reaction in aqueous, sustainable condition.