Ring-Opening of Cyclic Carbonates: From Fine Chemicals to CO2-based Polymers

Identifier:  TDX:4341

Handle: https://hdl.handle.net/20.500.11797/TDX4341

Authors:  Ni, Jixiang

Abstract:
The main objective of this doctoral thesis was the development of the novel ring-opening reactions of cyclic carbonates acting as substrates. Cyclic carbonates have unique reactivity comprising both nucleophilic and electrophilic sites. This dual behavior allows expanding the portfolio of functional intermediates and monomers derived from a CO2-derived heterocycle. So far, the ring-opening chemistry of these heterocycles has been mostly limited to carbonate-attack approaches, which are useful in the context of fine-chemical (linear carbamates) and polymer chemistry (polyurethanes) applications. Much less explored are nucleophilic attacks on positions that are referred to as “methylene” and “exo-cyclic” in the cyclic carbonate precursor, and new approaches that can unleash effective and selective protocols for such pathways will help to increase the applicability of these CO2 based heterocycles in synthetic chemistry. Several new types of ring-opening processes have been studied in this thesis and details of these advancements are described below. Generally concluding, the results presented in this thesis show that (functionalized) cyclic carbonates are versatile synthons for the preparation of a wide variety of new and functional heterocyclic products, and aliphatic polycarbonates.