AgI /TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones

Xue-Dong Li; Qing-Wen Song; Xian-Dong Lang; Yao Chang; Liang-Nian He

doi:10.1002/cphc.201700297

Ag^I /TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones

Chemphyschem. 2017 Nov 17;18(22):3182-3188. doi: 10.1002/cphc.201700297. Epub 2017 May 23.

Authors

Xue-Dong Li¹, Qing-Wen Song¹, Xian-Dong Lang¹, Yao Chang¹, Liang-Nian He^{1

2}

Affiliations

¹ State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, P.R. China.
² Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin, 300071, P.R. China.

PMID: 28464505
DOI: 10.1002/cphc.201700297

Abstract

Chemical valorization of CO₂ to access various value-added compounds has been a long-term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one-pot three-component reaction of terminal propargyl alcohols, CO₂ , and 2-aminoethanols was developed for the synthesis of 2-oxazolidinones and an equal amount of α-hydroxyl ketones promoted by Ag₂ O/TMG (1,1,3,3-tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2-aminoethanol/CO₂ coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2-aminoethanol through the formation of hydrogen bonds and also activate CO₂ .

Keywords: C1 building blocks; carbon dioxide chemistry; cyclization; homogeneous catalysis; synthetic methods.