4,4-Dimethyl-3,5,8-trioxabicyclo[5.1.0]octane is used in the CO2-mediated formation of chiral carbamates from meso-epoxides via polycarbonate intermediates and amine nucleophiles, which opens up a wide a wide range of CO2-based carbamate scaffolds with excellent yields and 99% enantiomeric excess.