CO₂ Adducts of Phosphorus Ylides: Highly Active Organocatalysts for Carbon Dioxide Transformation

Abstract

A series of phosphorus ylide (P-ylide) CO2 adducts were synthesized and first used as organocatalysts for CO2 transformation. Detailed studies on the cycloaddition reaction of CO2 with terminal epoxides show that P-ylide CO2 adducts are efficient metal-free and halogen-free organocatalysts to mediate this reaction under ambient conditions (25 °C, 1 atm of CO2). More importantly, the reactions proceeded with a broad scope, high efficiency, and good functional group tolerance and the corresponding cyclic carbonate products were obtained in good to excellent yields (46–99%). Meanwhile, the kinetic study by in situ FTIR methods suggested an intermolecular cooperation effect for effectively accelerating the ring opening of terminal epoxides. Furthermore, from an investigation of the catalytic diversity of P-ylide CO2 adducts, CO2 also could be converted to functionalized cyclic α-alkylidene carbonates, oxazolidinone, and N-methylated and N-formylated amines by organocatalytic reactions.