MODULAR APPROACH TO CHIRAL PYRIDINE CONTAINING MACROCYCLES: SYNTHESIS, CHARACTERIZATION, REACTIVITY AND CATALYTIC ACTIVITY OF THEIR METAL COMPLEXES

In this thesis is reported a simple, fast, economic modular approach for the synthesis of chiral tetraaza-macrocycles containing a pyridine ring (Pc-L*) starting from aminoacids. The characterization of the ligands and of their complexes with copper (I) and silver (I) salts also descrive, including several crystal suitable for X-ray determination. The organometallic reactivity and coordination behavior of these complexes with CO and acetonitrile has been studied. The complexes were succesfully applied as catalysts for cyclopropanation and A3-coupling reaction and for the synthesis of isochromenes starting from propargyl-aldehydes. In any case, excellent results in terms of yields and chemoselectivity were obtained and, concerning the cyclopropanation reaction, very good enantioselectivities on different substrates were achieved. Furthermore, a new class of Pc-L* ligands potentially dianionic is described and the complexation studies of these macrocycles with ruthenium, cobalt, zyrconium and iron are reported.