N-Heterocyclic carbene-mediated zwitterionic polymerization of N-substituted N-carboxyanhydrides toward poly(α-peptoid)s: kinetic, mechanism, and architectural control.

N-Heterocyclic carbene (NHC)-mediated polymerizations of N-butyl N-carboxyanhydride (Bu-NCA) to produce cyclic poly(N-butyl glycine)s (c-NHC-PNBGs) have been investigated in various solvents with NHCs having differing steric and electronic properties. Control over the polymer molecular weight (MW) and polymerization rate is strongly dependent on the solvent and the NHC structure. Kinetic studies reveal that the propagating intermediates for the polymerization in low dielectric solvents (e.g., THF or toluene) maintain cyclic architectures with two chain ends in close contact through Coulombic interaction. The NHCs not only initiate the polymerization, but also mediate the chain propagation as intramolecular counterions. Side reactions are significantly suppressed in low dielectric solvents due to the reduced basicity and nucleophilicity of the negatively charged chain ends of the zwitterions, resulting in quasi-living polymerization behavior. By contrast, the two charged chain ends of the zwitterionic species are fully dissociated in high dielectric solvents. The chain propagation proceeds as in conventional anionic polymerizations, wherein side reactions (e.g., transamidation) compete with chain propagation, resulting in significantly diminished control over polymer MW. The cyclic zwitterionic propagating species can be converted into their linear polymeric analogues (l-NHC-PNBGs) by end-capping with electrophiles (e.g., acetyl chloride) or the NHC-free cyclic analogues (c-PNBGs) by treatment with NaN(TMS)(2), as evidenced by MALDI-TOF MS, NMR, and SEC analysis.