Development of novel bio-based building blocks and their application in organic synthesis and materials science

Description

In the progression of modern society, the inevitable exhaustion of fossil resources becomes an increasingly concerning matter. These resources are not only the basis of the energy production of the world but also the precursor for many important platform chemicals. Therefore, development of green and renewable alternatives to the chemicals used in the current industry has become necessary. Within this context, the aim of the present thesis was the development of new efficient methodologies for obtaining high added-value products starting from biomass, a renewable source. The bio-based building blocks obtained were subsequently employed for the synthesis of polyfunctionalized chemicals and of polymers. The first part of the thesis focuses on the utilization of a bio-based meso diol for the synthesis of sugar derived structures, through the coupling of biocatalysis and multicomponent reaction (MCRs). These two different approaches are able to satisfy the requirements of an ideal approach, regarding selectivity (stereocontrol), efficiency and sustainability and their union with renewable feedstocks in a single integrated general strategy represents a powerful tool to achieve a sustainable synthesis. In particular, the work focused on the synthetic elaboration of the chiral molecules obtained through enzymatic desymmetrization to give enantiomerically pure building blocks to be used in diastereoselective Passerini reactions. In order to establish the synthetic usefulness of this new method, we demonstrated its application to the diversity-oriented synthesis of chiral, bio-based, oxygen heterocycles and to the target-oriented synthesis of Bengamides, a wide family of natural products of marine origin. The second part of the thesis is dedicated to the synthesis of a lactam- based monomer derived from bio-based starting materials and its subsequent polymerization. The project involved the synthesis and polymerization of 3-methylene-2-piperidone (3M2Pip) monomers, targeting the synthesis of well-defined hydroxyl end functional P(3M2Pip), i.e. HO-P(3M2Pip). Once obtained end-functionalized 3M2Pip-based polymers we will use them as a macro-initiator for the synthesis of degradable polyester second blocks, applicable in drug delivery polymer materials.

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