CO2 -Sourced α-Alkylidene Cyclic Carbonates: A Step Forward in the Quest for Functional Regioregular Poly(urethane)s and Poly(carbonate)s.

Described is a robust platform for the synthesis of a large diversity of novel functional CO2 -sourced polymers by exploiting the regiocontrolled ring-opening of α-alkylidene carbonates by various nucleophiles. The reactivity of α-alkylidene carbonates is dictated by the exocyclic olefinic group. The polyaddition of CO2 -sourced bis(α-alkylidene carbonate)s (bis-αCCs) with primary and secondary diamines provides novel regioregular functional poly(urethane)s. The reactivity of bis-αCCs is also exploited for producing new poly(β-oxo-carbonate)s by organocatalyzed polyaddition with a diol. This synthesis platform provides new functional variants of world-class leading polymer families (polyurethanes, polycarbonates) and valorizes CO2 as a chemical feedstock.