A very unusual role of polystyrene stabilized rhodium (Rh@PS) nanoparticles as a supported catalyst is described for “reverse-esterification” of ethanol with benzyl/alkyl alcohols or aldehydes. Faster and selective oxidation of ethanol to acetaldehyde and H2 under Rh@PS catalyzed conditions which restricted further oxidation of benzyl/alkyl alcohols and their in situ reaction gave the corresponding acetate esters following the dehydrogenative-coupling approach. A hitherto redox dehydrogenative-coupling of ethanol and aldehydes has also been explored for the same acetate ester synthesis under Rh@PS catalyzed conditions.
