Carboxylative cyclization of propargyl alcohols with carbon dioxide for the synthesis of α-alkylidene cyclic carbonates in presence of Co(III) schiff base complex catalyst

A cobalt(III) complex, [Co(L)3](DMF) (1) of Schiff base ligand HL, 2-((E)-(benzylimino)methyl)-4-bromophenol is prepared and single crystal X-ray structural analysis have also been performed. The structures of complex 1 showed hexa-coordinated mononuclear systems that adopt octahedral geometry. The complex has also exhibited the supramolecular networks through non-covalent interactions like H-bonding, C–H...π stacking. Moreover, the complex 1 is very effective in the catalytic fixation of carbon dioxide in propergyl alcohols to produce α-alkylidene cyclic carbonates. The catalytic production of α-alkylidene cyclic carbonates have been carried out through carboxylative cyclization of propargyl alcohols using CO2 balloon of 1 atm pressure at 80°C. Solvent free condition (green synthesis) made this catalytic protocol eco-friendly towards the environment. Utilizing various substrates of propargyl alcohols moderate to high percentage yield (62-95%) of respective α-alkylidene cyclic carbonates product have been isolated over this catalytic reaction. Besides, the theoretical calculations (DFT) was performed for the prediction of probable mechanism of the catalytic reaction.