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

The first cascade reaction between CO2‐sourced α‐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.