Coupling Reactions Between Aromatic Carbon - and Nitrogen - Nucleophiles and Electrophiles: Reaction Intermediates, Products and their Properties

During my PhD I was involved in many studies concerning the nucleophilic (SNAr) and electrophilic (SEAr) aromatic substitution reactions. My research activity was focused on the study of different electrophile/nucleophile combinations between strongly activated species, with the purpose to investigate on their reactivity, to detect new intermediates of the aromatic substitution reaction and to obtain new higly conjugated structures bearing contemporaneously electron donor and acceptor moieties on the same unit for application in different fields. Different reactions between both neutral or charged electrophilic and nucleophilic species were performed and from their combinations new products for applications in different fields (e.g. medicine, biology and materials) were obtained and new intermediates of the aromatic substitution reactions [e.g. Wheland (W), Meisenheimer (M), and even Wheland-Meisenheimer (WM)], were detected and characterized, mainly using NMR spectroscopic techniques. In particular the involved nucleophilic species were: tri- and diaminobenzene derivatives, trihydroxybenzene, trimethoxybenzene, anisole derivatives and aminothiazole derivatives; whereas the selected electrophilic species were: aryldiazonium ions, benzofuroxan and benzofurazan derivatives, thiophene derivatives and benzhydrylium ions. Furthermore, the last year of my PhD course, I spent a period in the Department of Chemistry, Ludwig-Maximilians-University of Munich, in collaboration with Prof. Herbert Mayr’s group, with the aim to investigate on the nucleophilic reactivities of di- and triaminobenzene derivatives performing their combination with different reference electrophiles, selected from the Mayr’s reactivity scales.