Cascade Transformation of Carbon Dioxide and Alkyne-1,n-diols into Densely Substituted Cyclic Carbonates

A silver-catalyzed cascade conversion of modular alkyne-1,n-diols and carbon dioxide has been developed allowing for the selective formation of keto-functionalized cyclic carbonates. The protocol is characterized by its operational simplicity, excellent scope of carbonate-based heterocycles, and mild reaction conditions. In situ IR studies, control experiments, and detailed computational analysis of these manifolds reveal the intermediacy of an α-alkylidene carbonate that is intercepted by an intramolecular alcohol nucleophile. The synthetic potential of this conceptually attractive CO2 transformation is demonstrated in the preparation of larger ring carbonates and their thermal rearrangement to sterically crowded, five-membered fused carbonate products.