Zunino, Rachele (2025) Organocatalysis for Polymer Synthesis. [Tesi di dottorato]

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Abstract

This doctoral thesis presents the main outcomes of the research I carried out during my PhD, which was primarily focused on the study of ring-opening polymerization (ROP) reactions promoted by metal-free catalysts. The work integrates experimental and computational approaches to design highly active and selective organocatalysts for the synthesis of sustainable materials. Particular emphasis is placed on the computational component, through which reliable models were developed to rationalize experimental observations and guide future catalyst design, providing a deeper understanding of the factors governing catalytic activity and selectivity. To orient the reader, the thesis begins with an introduction outlining the fundamental concepts of organocatalysis, its application to ring-opening polymerization, and the role of computational modelling in the study of catalytic mechanisms. It is then organized into four chapters, each presenting one of the main research topics developed during my doctoral studies. The first two chapters describe combined experimental and theoretical studies on metal-free bifunctional catalysts designed for the ring-opening (co)polymerization of cyclic monomers. The third chapter presents a DFT study of the ROP of rac- and meso-lactide, aimed at developing a theoretical model to elucidate the origin of stereocontrol in ROP promoted by thiourea–amine based catalysts. Finally, the fourth chapter presents studies that extend beyond organocatalyzed ROP reactions. It includes the results of my first published work, a computational investigation of the chain-shuttling mechanism, which introduced me to and deepened my interest in computational chemistry, along with a preliminary benchmarking study on single-step organocatalytic reactions.

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