The project aims at investigating new frontiers in the field of organocatalysis, and it targets the design and realization of catalytic batch and flow systems for enantioselective organocatalytic synthesis, using immobilized catalysts and co-catalysts. Covalently immobilized, smart organocatalysts will be realized, fully characterized and employed in challenging enantioselective reactions. Heterogeneous systems combine in a useful enabling platform leading to valuable chiral, small organic molecules (drugs, agrochemicals) in highly enriched enantiomeric forms, and their use under flow mode conditions is considered a promising green procedures with potential for intensification. The project is focused around the following "tools": 1) mesoporous silica, monolithic polymers with dual micro- and meso-porosity, all with tunable surface chemistry and amenable for chemical functionalization; 2) chiral organonocatalysts based on chinconan alkaloids and acidic co-catalysts; 3) electrospray ionization mass spectrometry ESI-MS for screening the reactivity of catalysts, monitoring organic and organometallic reactions by detection of reactants, intermediates and products and eventually elucidation of reaction mechanism. Innovative immobilization strategies of privileged chiral organocatalysts (cinchonan derivatives, 1,2-diamines) on porous solids will be investigated, including incremental approaches for the sequential surface-grafting of both catalyst and acidic co-catalyst. These systems will be evaluated for their ability to catalyze Michael addition reactions, leading to chiral products with two stereocenters. In order to shed light on the reaction machinery, a computational approach combined with advanced ESI-MS techniques will be adopted. The combination of experimental evidences, spectroscopic analyses and computational rationalizations would lead to an iterative process enabling a faster convergence to optimal reaction conditions.
