Cooperative Catalysis of Ru(III)‐Porphyrin in CO₂‐Involved Synthesis of Oxazolidinones

Abstract

CO2‐transformations into high value‐added products have become a fascinating area in green chemistry. Herein, a Ru(III)‐porphyrin catalyst (RuCl3 ⋅ 3H2O−H2TPP) was found highly efficient in the three‐component reaction of CO2, aliphatic amines and dichloroethane (or its derivative) for synthesis of oxazolidinones in the yields of 71∼91%. It was indicated by means of the control experiments and UV‐vis spectra that CO2 was stoichiometrically activated by the involved aliphatic amine substrates to form a stable carbamate salt while 1,2‐dichloroethane (or its derivative) was independently activated by the involved Ru(III)‐porphyrin catalyst. The combination of CO2‐activation by aliphatic amines with 1,2‐dichloroethane activation by Ru(III)‐porphyrin catalyst cooperatively contributed to this successful transformation.

Facile Multicomponent Synthesis of Oxazolidinones from Primary Amines and Cesium (Hydrogen)Carbonate

“…In this procedure, 10 atm of carbon dioxide, DCE, cesium carbonate as a base, and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as a catalyst were used [16] . Finally, aliphatic amines were converted into oxazolidinones based on the usage of 10 atm of carbon dioxide, DCE, and a ruthenium complex catalyst [17] . Carbonate salts as C1 feedstock instead of carbon dioxide are known for a long time but have so far only rarely been applied to the synthesis of oxazolidinones.…”

“…[16] Finally, aliphatic amines were converted into oxazolidinones based on the usage of 10 atm of carbon dioxide, DCE, and a ruthenium complex catalyst. [17] Carbonate salts as C1 feedstock instead of carbon dioxide are known for a long time but have so far only rarely been applied to the synthesis of oxazolidinones. For example, propargyl amines and silyl alkynyl bromides have been used as starting materials in a palladium-catalyzed protocol with cesium hydrogencarbonate replacing carbon dioxide.…”

The efficient CO2 fixation catalyzed by K‐doped g‐C3N4 catalyst for synthesizing benzimidazoles at atmospheric pressure

“…Among them, CO 2 capture and fixation is an effective solution to environmental problems. The conversion of CO 2 to valuable organic compounds has received extensive attention in recent years, including benzimidazole, 3 dimethyl carbonate, 4 oxazolidinone, 5 methanol, 6 urea, 7 formic acid, 8 etc. Whereas CO 2 is thermodynamically stable and kinetically inert as a linearly symmetric molecule, making it difficult to convert into valuable chemicals 9 .…”

Modulating the Energetics of C–H Bond Activation in Methane by Utilizing Metalated Porphyrinic Metal–Organic Frameworks

“…Metalloporphyrin complexes of groups 8 and 9 have been synthesized and are well-known for catalyzing various types of organic transformations. − However, synthesis of metalloporphyrins is difficult and is prone to oxidative self-destruction. Better utilization of metalloporphyrins can be made by immobilizing them onto polymers or onto MOFs.…”