Unprecedented Concomitant Formation of Cu₂O-CD Nano-Superstructures During the Aerobic Oxidation of Alcohols and...

Copper-cyclodextrins (CDs)-catalyzed aerobic oxidation of alcohols under aqueous conditions and a concomitant formation of Cu₂O-cyclodextrin nano-superstructures (Cu₂O-CD nps) during the reaction are reported. The use of affordable copper and cyclodextrin combination for aerobic oxidation precluding organic solvents makes it a benign methodology. Intriguingly, a diverse array of Cu₂O-CD nps with unique morphologies was obtained by varying copper salts, cyclodextrins, and bases. The nano-superstructures were characterized by different techniques, such as X-ray diffraction, X-ray photoelectron spectroscopy, differential scanning calorimetry-thermogravimetric analysis, scanning electron microscopy, time of flight secondary-ion mass spectrometry, and transmission electron microscopy to confer their authenticity. Interestingly, the nano-superstructures showed promising catalytic efficiency for a one-pot three-component propargylamination reaction. The used particles were found to be recoverable and recyclable for propargylamination for up to three cycles, with no loss of catalytic activity. Moreover, the concomitant formation of Cu₂O-CD nanostructures and their self-segregation during an aerobic oxidation reaction under homogenous conditions is a first-of-its-kind method depicting simultaneous catalysis and metal waste valorization (SCMWV). Overall, this new approach of reaping the benefits of homogenous metal catalysis and simultaneously sequestrating the metal into a high-value product might pave the way to develop many such SCMWV protocols in future.