Che vinca il più Forte. Proposta di traduzione, analisi e commento di "Wojna polsko-ruska pod flagą biało-czerwoną" di Dorota Masłowska.

Traduzione dal polacco in italiano - accompagnata da analisi e commento dei temi proposti - di alcuni estratti dal bestseller della scrittrice polacca adolescente, che racconta il mondo visto dagli occhi di un giovane disoccupato poco istruito di provincia. Un'immagine cruda e senza filtri della gioventù in Polonia negli anni di transizione dalla caduta del muro di Berlino all'ingresso nell'Unione Europea. Un momento storico impossibile da collocare nella ripetitività tipica dei grandi avvenimenti in Polonia, vissuto direttamente sulla pelle dei suoi protagonisti, cioè i giovani senza né passato né futuro, incapaci di coltivare il presente.

α-ossidazione asimmetrica organocatalizzata di aldeidi ramificate con dibenzoil perossido

In this thesis, the development of an enantioselective oxidation of α-branched aldehydes using covalent organocatalysis is described. At state of the art, the asymmetric organocatalysis approach, gave often serous difficulties for these kind of substrate respect “classic” aldehydes. We have used a primary cinchona alkaloid derived amine (specially the 9-epi-NH2-CDA) to develop the reaction in combinations with additives. With benzoyl peroxide as oxidant and 2-phenylpropionaldehyde as reference substrate, we have tried to optimize this system but we not found great results about enantiomeric excess.

Beyond simple proton transfer processes: domino reactions between 4-substituted indoles and nitroethene as a new gateway to ergot alkaloids

The multimodal biology activity of ergot alkaloids is known by humankind since middle ages. Synthetically modified ergot alkaloids are used for the treatment of various medical conditions. Despite the great progress in organic syntheses, the total synthesis of ergot alkaloids remains a great challenge due to the complexity of their polycyclic structure with multiple stereogenic centres. This project has developed a new domino reaction between indoles bearing a Michael acceptor at the 4 position and nitroethene, leading to potential ergot alkaloid precursors in highly enantioenriched form. The reaction was optimised and applied to a large variety of substrate with good results. Even if unfortunately all attempts to further modify the obtained polycyclic structure failed, it was found a reaction able to produce the diastereoisomer of the polycyclic product in excellent yields. The compounds synthetized were characterized by NMR and ESIMS analysis confirming the structure and their enantiomeric excess was determined by chiral stationary phase HPLC. The mechanism of the reaction was evaluated by DFT calculations, showing the formation of a key bicoordinated nitronate intermediate, and fully accounting for the results observed with all substrates. The relative and absolute configuration of the adducts were determined by a combination of NMR, ECD and computational methods.