Organocatalytic Cascade Synthesis of Peroxy-Substituted Cyclic Carbonates from CO2-Sourced α-Alkylidene Cyclic Carbonates and Hydroperoxides

The first cascade reaction between CO2-sourced alpha-alkylidene cyclic carbonates and hydroperoxides is reported. This reaction proceeds smoothly under mild reaction conditions using 1,5,7-triazabicyclo[4.4.0]dec-5-ene as an effective commercially available organocatalyst, thus providing a sustainable methodology for the formation of a wide variety of peroxy-substituted cyclic carbonates in moderate to high yields. Control experiments, in situ FTIR measurements, and density functional theory calculations reveal that the catalytic reaction is a three-step process, including intermolecular transesterification, peroxyhemiacetalization, and intramolecular transesterification, with the second step being rate determining.

Automated summary

The first cascade reaction between CO2-sourced cyclic carbonates and hydroperoxides is reported using an effective commercially available organocatalyst, providing a sustainable method for the formation of peroxy-substituted cyclic carbonates.