Twisted amides have long been studied in physical organic chemistry due the unusual reactivity profiles that emerge from the reduced resonance interaction between the nitrogen atom and the neighboring carbonyl group. Our laboratory has recently leveraged the heightened nucleophilicity found in twisted amide structures to develop a new living polymerization that proceeds through a covalent electrophilic mechanism termed halide-rebound polymerization. This presentation will explore how simple substitution effects can be used to tune the geometric distortion of the amide, leading to significant changes in monomer reactivity. In addition, halide and solvent effects on the polymerization reaction will be highlighted as a means to tune monomer reactivity and alter the rate-limiting steps of the halide-rebound process. Through greater understanding of the polymerization mechanism through kinetic studies and computational prediction of the ground state geometries, new monomers with enhanced performance have been designed to improve the livingness of the polymerization.

Tuning the twist in amide monomers for halide-rebound polymerization

ACS Spring Meeting 2021

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