Efficient Ionic-Liquid-Promoted Chemical Fixation of CO2 into α-Alkylidene Cyclic Carbonates

The efficient conversion of CO2 into value-added chemicals under metal-free conditions is of significant importance from the viewpoint of sustainable chemistry. In this work, ionic liquids (ILs) with different properties were used to promote the reaction between CO2 and propargylic alcohol for the synthesis of alpha-alkylidene cyclic carbonates. The protic IL 1,8-diazabicyclo-[ 5.4.0]-7-undecenium 2-methylimidazolide ([DBUH][ MIm]) was prepared by simple neutralization of the superbase with a weak proton donor and could efficiently promote the reactions in high yields. After the reactions, the IL was separated from the reaction mixtures by simply adding water, and then reused after drying without an observable decrease in the catalytic activity and selectivity. NMR spectroscopy and detailed density functional theory analysis were used to propose a reaction mechanism. Both the cation and anion of the IL played a key synergistic role in promoting the reaction. These findings may be useful for the rational design of novel metal-free and recyclable routes for the reaction between CO2 and propargylic alcohols.