Stereoconvergent Ring-Opening Polymerizations via Palladium-Catalyzed Asymmetric Allylic Substitution

Current synthetic methods to access stereoregular organic polymeric materials through chiral racemic monomer pools often operate through kinetic resolutions which restrict maximum polymer yield to 50%. This thesis discusses the development and challenges of the design of a novel methodology to access stereoregular polymers through stereoconvergence of chiral racemic monomers. The mechanism is derivative of transition-metal catalyzed asymmetric allylic substitution, pioneered by Trost, Carreira, and several others. While the mechanism of stereoconvergence in this chemistry is highly catalyst and substrate-dependent, palladium-catalyzed systems which are employed throughout the work herein are well understood and predominately proceed through a stereoablated prochiral π-allyl complex. This work discusses the optimization of several unexpected difficulties of a palladium-catalyzed asymmetric allylic substitution polymerization, including molecular weight control and inherent stereochemical bias of the polymer chain-end. Additionally, NMR spectroscopy studies are performed to streamline the quantification of tacticity of a novel polymer.