Enabling Control over Heteroatom Enriched Polymers via Asymmetric Allylic Amination

Allylic amination polymerization was developed to enable the controlled synthesis of heteroatom enriched polymers with tunable properties. This method leverages asymmetric catalysis to facilitate oxidative addition of chiral racemic vinyl aziridines, revealing a stereoablated ambiphilic -allyl complex, having two electrophilic sites available for selective allylic amination. Subsequent propagations are directed by the catalyst under enantiomorphic site control, where catalyst architecture defines polymer regiochemistry and tacticity.In this thesis, asymmetric allylic amination polymerizations are expanded to encapsulate 1-tosyl-2-vinylazetidine as a suitable monomer choice for this methodology. It was found throughout this work that small changes in monomer structure influence catalyst reactivity in polymerization, hence differences in the regio- and stereochemical outcomes are shown. The synthesis of linear C5N1 polyamines was accomplished, with demonstration of alkene stereoenrichment not seen in previous work with aziridines. Development of new methodology employing iridium catalysis was necessary to access the branched C3N1 microstructure.