Silver(I)-Catalyzed Three-Component Reaction of Propargylic Alcohols, Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β-Oxopropyl Carbonates

Zhi-Hua Zhou; Qing-Wen Song; Jia-Ning Xie; Ran Ma; Liang-Nian He

doi:10.1002/asia.201600600

Silver(I)-Catalyzed Three-Component Reaction of Propargylic Alcohols, Carbon Dioxide and Monohydric Alcohols: Thermodynamically Feasible Access to β-Oxopropyl Carbonates

Chem Asian J. 2016 Jul 20;11(14):2065-71. doi: 10.1002/asia.201600600. Epub 2016 Jun 27.

Authors

Zhi-Hua Zhou¹, Qing-Wen Song¹, Jia-Ning Xie¹, Ran Ma¹, Liang-Nian He^{2

3}

Affiliations

¹ State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P.R. China.
² State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P.R. China. heln@nankai.edu.cn.
³ Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300071, P.R. China. heln@nankai.edu.cn.

PMID: 27237704
DOI: 10.1002/asia.201600600

Abstract

A silver(I)-catalyzed three-component reaction of propargylic alcohols, CO2 , and monohydric alcohols was successfully developed for the synthesis of β-oxopropyl carbonates. As such, a series of β-oxopropyl carbonates were exclusively produced in excellent yields (up to 98 %), even under atmospheric pressure of CO2 . The silver catalyst works efficiently for both the carboxylative cyclization of propargylic alcohols with CO2 and subsequent transesterification of α-alkylidene cyclic carbonates with monohydric alcohols; thus this tandem process performs smoothly under mild conditions. This work provides a versatile and thermodynamically favorable approach to dissymmetric dialkyl carbonates.

Keywords: carbonates; homogeneous catalysis; multicomponent reactions; silver; synthesis design.