Acqua: solvente elettivo in Organocatalisi e Biocatalisi

Water is a safe, harmless, and environmentally benign solvent. From an eco-sustainable chemistry perspective, the use of water instead of organic solvent is preferred to decrease environmental contamination. Moreover, water has unique physical and chemical properties, such as high dielectric constant and high cohesive energy density compared to most organic solvents. The different interactions between water and substrates, make water an interesting candidate as a solvent or co-solvent from an industrial and laboratory perspective. In this regard, organic reactions in aqueous media are of current interest. In addition, from practical and synthetic standpoints, a great advantage of using water is immediately evident, since it does not require any preliminary drying process. This thesis was found on this aspect of chemical research, with particular attention to the mechanisms which control organo and bio-catalysis outcome. The first part of the study was focused on the aldol reaction. In particular, for the first time it has been analyzed for the first time the stereoselectivity of the condensation reaction between 3-pyridincarbaldehyde and the cyclohexanone, catalyzed by morpholine and 4-tertbutyldimethylsiloxyproline, using water as sole solvent. This interest has resulted in countless works appeared in the literature concerning the use of proline derivatives as effective catalysts in organic aqueous environment. These studies showed good enantio and diastereoselectivities but they did not present an in depth study of the reaction mechanism. The analysis of the products diastereomeric ratios through the Eyring equation allowed to compare the activation parameters (ΔΔH≠ and ΔΔS≠) of the diastereomeric reaction paths, and to compare the different type of catalysis. While morpholine showed constant diasteromeric ratio at all temperatures, the O(TBS)-L-proline, showed a non-linear Eyring diagram, with two linear trends and the presence of an inversion temperature (Tinv) at 53 ° C, which denotes the presence of solvation effects by water. A pH-dependent study allowed to identify two different reaction mechanisms, and in the case of O(TBS)-L-proline, to ensure the formation of an enaminic species, as a keyelement in the stereoselective process. Moreover, it has been studied the possibility of using the 6- aminopenicillanic acid (6-APA) as amino acid-type catalyst for aldol condensation between cyclohexanone and aromatic aldehydes. A detailed analysis of the catalyst regarding its behavior in different organic solvents and pH, allowed to prove its potential as a candidate for green catalysis. Best results were obtained in neat conditions, where 6-APA proved to be an effective catalyst in terms of yields. The catalyst performance in terms of enantio- and diastereo-selectivity, was impaired by the competition between two different catalytic mechanisms: one via imine-enamine mechanism and one via a Bronsted-acid catalysis. The last part of the thesis was dedicated to the enzymatic catalysis, with particular attention to the use of an enzyme belonging to the class of alcohol dehydrogenase, the Horse Liver Alcohol Dehydrogenase (HLADH) which was selected and used in the enantioselective reduction of aldehydes to enantiopure arylpropylic alcohols. This enzyme has showed an excellent responsiveness to this type of aldehydes and a good tolerance toward organic solvents. Moreover, the fast keto-enolic equilibrium of this class of aldehydes that induce the stereocentre racemization, allows the dynamic-kinetic resolution (DKR) to give the enantiopure alcohol. By analyzing the different reaction parameters, especially the pH and the amount of enzyme, and adding a small percentage of organic solvent, it was possible to control all the parameters involved in the reaction. The excellent enatioselectivity of HLADH along with the DKR of arylpropionic aldehydes, allowed to obtain the corresponding alcohols in quantitative yields and with an optical purity ranging from 64% to >99%.

Biomasse e loro quantificazione economica per un efficiente uso dell'energia

Biomasses and their possible use as energy resource are of great interest today, and the general problem of energy resources as well. In the present study the key questions of the convenience, from both energy and economy standpoints, have been addressed without any bias: the problem has been handled starting from “philosophical” bases disregarding any pre-settled ideology or political trend, but simply using mathematical approaches as logical tools for defining balances in a right way. In this context quantitative indexes such as LCA and EROEI have been widely used, together with multicriteria methods (such as ELECTRE) as decision supporting tools. This approach permits to remove mythologies, such as the unrealistic concept of clean energy, or the strange idea of biomasses as a magic to solve every thing in the field of the energy. As a consequence the present study aims to find any relevant aspect potentially useful for the society, looking at any possible source of energy without prejudices but without unrealistic expectations too. For what concerns biomasses, we studied in great details four very different cases of study, in order to have a scenario as various as much we can. A relevant result is the need to use biomasses together with other more efficient sources, especially recovering by-products from silviculture activities: but attention should be paid to the transportation and environmental costs. Another relevant result is the very difficult possibility of reliable evaluation of dedicated cultures as sources for “biomasses for energy”: the problem has to be carefully evaluated case-by-case, because what seems useful in a context, becomes totally disruptive in another one. In any case the concept itself of convenience is not well defined at a level of macrosystem: it seems more appropriate to limit this very concept at a level of microsystem, considering that what sounds fine in a limited well defined microsystem may cause great damage in another slightly different, or even very similar, microsystem. This approach seems the right way to solve the controversy about the concept of convenience.