Silver(I)-Promoted Cascade Reaction of PropargylicAlcohols Carbon Dioxide and Vicinal Diols: Thermodynamically FavorableRoute to Cyclic Carbonates

摘要

A silver(I)-promoted cascade reaction was developed for the synthesis of cyclic carbonates from terminal propargylic alcohols, carbon dioxide, and vicinal diols. Compared with direct condensation of vicinal diols with CO2, this protocol provides a thermodynamically favorable route to cyclic carbonates and α-hydroxyl ketones in excellent yields (up to 97%) without the additional dehydration step. Such a cascade procedure proceeds presumably through initial reaction of propargylic alcohol with CO2 and subsequent nucleophilic attack of vicinal alcohol on in situ-formed α-alkylidene cyclic carbonate, resulting in successive generation of α-alkylidene cyclic carbonate, unsymmetrical β-oxoalkyl carbonate, cyclic carbonate, and α-hydroxyl ketone.