Silver(I)-Promoted Cascade Reaction of Propargylic Alcohols, Carbon Dioxide, and Vicinal Diols: Thermodynamically Favorable Route to Cyclic Carbonates

Zhi-Hua Zhou; Qing-Wen Song; Liang-Nian He

doi:10.1021/acsomega.6b00407

Silver(I)-Promoted Cascade Reaction of Propargylic Alcohols, Carbon Dioxide, and Vicinal Diols: Thermodynamically Favorable Route to Cyclic Carbonates

ACS Omega. 2017 Jan 31;2(1):337-345. doi: 10.1021/acsomega.6b00407.

Authors

Zhi-Hua Zhou¹, Qing-Wen Song¹, Liang-Nian He¹

Affiliation

¹ State Key Laboratory and Institute of Elemento-Organic Chemistry and Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, No. 94, Weijin Road, Nankai District, Tianjin 300071, P. R. China.

Abstract

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.