Computational Investigations of Catalyzed Organic Reactions: Carbocatalysis, Biocatalysis, Metal and Organo Catalysis

This thesis comprises most of the computational results obtained during the three year Chemistry Ph.D course, during which the research activity mainly focused on investigating catalyzed reaction mechanisms. Catalysis is a vast phenomenon and this dissertation does not presume to cover its extent, nor to be a mere list of computational investigations. The purpose is to stress out that computational organic chemistry is a tool to be exploited to explain how and why some reactions prefer to cover one path rather than another by interpreting computation outcomes. Among the immense world of catalysts, the activity of carbon nanoparticles, enzymes, metal complex and proline in catalyzed organic reactions were investigated. Commercially available software for molecular computations were used to carry out the investigations. The thesis is divided in few parts; the former (Part I) provides some insights into the computational methods used during the PhD activity where Quantum-Mechanics (QM), Molecular-Mechanics (MM) and hybrid QM/MM methods are briefly described. Parts II-V gather the results obtained during the PhD activity. In Part II, two examples of carbo-catalyzed reactions are reported, while Part III and IV collect the computational evidences achieved by analysing the reaction mechanism of enzymatic and metal- (or organo-) catalyzed reactions respectively. The last Part (V) includes two, among the many, side works that were carried out during the PhD course. A résumé of the computational results is reported in Part VI.