Catalytic fluoride triggers dehydrative oxazolidinone synthesis from CO₂

Abstract

Herein, catalytic fluoride (F À ) is demonstrated to be a trigger for dehydrative immobilization of atmospheric pressure CO 2 , such that reaction of CO 2 with b-amino alcohols derived from natural amino acids gives optically pure oxazolidinones in high yields. A synergistic combination of fluoride and organosilicon agents (e.g., Bu 4 NF + Ph 3 SiF or siloxanes) enhances the catalytic activity and functional group compatibility. This system lies at the interface between homogenous and heterogeneous catalysis, and may prove useful for the development of recoverable/reusable siloxane-based CO 2 immobilization materials.

Antibiotics from Carbon Dioxide: Sustainable Pathways to Pharmaceutically Relevant Cyclic Carbamates

“…Additionally, a Lewis acid cocatalyst is sometimes employed to activate the carbonyl group, as shown in Schemeà. Examples of catalysts include ceria, alumina, fluoride, Cs 2 CO 3 ,, and various Sn species …”

“…Cyclization of amino alcohols and carbon dioxide with Lewis base (and Lewis acid) catalysts. [71b], , , [75b]…”

Ionic Liquid-Promoted Three-Component Domino Reaction of Propargyl Alcohols, Carbon Dioxide and 2-Aminoethanols: A Thermodynamically Favorable Synthesis of 2-Oxazolidinones

“…As the surrogate of CO, CO 2 is a more desirable material. Therefore, synthesis of 2-oxazolidinones using CO 2 and appropriate substrates has attracted much attention [ 14 , 39 , 40 ], among which the direct synthesis of oxazolidinones starting from 2-aminoethanols and CO 2 is considered as an ideal route because the aqueous amino alcohols have been widely utilized to capture CO 2 in industry [ 41 , 42 ]. Unfortunately, the direct reaction between amino alcohols and CO 2 occurs difficultly due to the thermodynamic limitation [ 43 ].…”

Ionic Liquid-Promoted Three-Component Domino Reaction of Propargyl Alcohols, Carbon Dioxide and 2-Aminoethanols: A Thermodynamically Favorable Synthesis of 2-Oxazolidinones

“…However, the conventional synthetic methods of 2-oxazolidinones rely on hazardous or expensive reagents such as isocyanides [36] and phosgene [37]. Recently, synthesis of 2-oxazolidinones using CO2 and appropriate substrates has attracted much attention [14,38,39], among which the direct synthesis of oxazolidinones starting from 2-aminoethanols and CO2 is considered as an ideal route because the aqueous amino alcohols have been widely utilized to capture CO2 in industry [40,41]. Unfortunately, the direct reaction between amino alcohols and CO2 occurs difficultly due to the thermodynamic limitation [42].…”