Utilizing Hypervalent Iodine(III) Reagents in the Synthesis of Dynamers and Functional Polymers.

摘要

Hypervalent iodine (HVI) reagents have been widely applied to organic transformations owing to their ability to undergo various redox and ligand exchange reactions. HVI compounds have also been employed in the synthesis of polymers, almost exclusively as polymerization initiators. This dissertation is focused on the utilization of HVI(III) reagents in the synthesis of various macromolecules. Symmetric bifunctional HVI compounds were introduced into polymer backbones via step-growth polymerization, chain-growth polymerization, or self-assembly processes. The polymers containing the HVI bonds were labile and participated in ligand exchange reactions in the presence of nucleophiles. As a result, these polymers were stimuli-responsive and dynamic, and underwent reversible structural transformations. Further, ligand exchange reaction at the HVI(III) center with nucleophiles, especially ones containing functional groups (e.g., azides, substituted carboxylates), provided a convenient source of functional radicals that were used in the polymerization of vinyl monomers or in the post-polymerization modification of polyunsaturated substrates. This method can be used to easily incorporatediverse functionalities in materials or to build up complex macromolecular architectures. Several synthetic approaches were developed utilizing HVI chemistry providing a versatile and robust tool for the production of advanced macromolecular materials.