Controlled Living Cascade Polymerization of Polycyclic Enyne Monomers: Leveraging Complete Degradability for a Stereochemical and Structural Investigation

Cascade polymerizations recently gained significant attention due to their use of unique transformations, involving multiple bond making and/or breaking steps, when converting monomers to repeat units. However, designing complex cascade polymerizations which proceed in a controlled manner is very challenging. Various side reactions can hamper polymerization performance and the efficiency of the cascade. In this work, we explore a metathesis-based cascade polymerization of unique polycyclic enyne monomers, which contain a terminal alkyne and two cyclic alkenes. By modifying the monomer's stereochemistry, linkers, and ring types, we were able to modulate the polymerization performance and the extent to which a complete cascade reaction occurs. Upon subjecting the resulting polymers to mild acidic conditions and analyzing the degradation products, we were able to calculate the percentage of repeat units derived from a complete cascade reaction (termed the cascade efficiency). In addition to identifying how various structural parameters in the monomer influence the success of a cascade polymerization, we were able to achieve controlled living cascade polymerizations of multiple monomers with >99% cascade efficiency and produce various block copolymers.

Automated summary

Cascade polymerization of unique polycyclic enyne monomers was explored, with modifications to monomer structure parameters allowing control over polymerization performance and efficiency. By analyzing degradation products under mild acidic conditions, the cascade efficiency could be calculated, leading to controlled living cascade polymerizations of multiple monomers with high efficiency.