Copolymerization of CO₂and meso epoxides using enantioselective β-diiminate catalysts: a route to highly isotactic polycarbonates

We report a new class of catalysts for the enantioselective copolymerization of CO2 and alicyclic meso epoxides. C1-Symmetric β-diiminate zinc catalysts were designed on the basis of mechanistic information and subsequently optimized using structure–activity relationships and iterative ligand design. The optimized catalysts yield highly isotactic poly(cyclohexene carbonate) and poly(cyclopentene carbonate) with units of up to 94% ee under mild conditions. A diblock copolymer of CO2/cyclohexene oxide and CO2/cyclopentene oxide was synthesized, demonstrating the controlled behaviour of the catalyst. Solid-state structures and solution-state dynamics of the catalyst were studied to explain trends in enantioselectivities and turnover frequencies. A strong correlation between the isotacticity of the polymer and its melting temperature was observed. X-ray powder diffraction was used to measure crystallinity and study the changes in morphology observed upon annealing.