Aerobic oxidation of α-hydroxy esters and phosphonates for direct formation of α-keto esters and α-keto phosphonates was explored using Au nanoparticle based catalytic systems. Alloying Au with Pd resulted in high activity and selectivity for the aerobic oxidation reaction under base and solvent free conditions. The formation of desired α-keto esters and α-keto phosphonates as sole products were highly dependent on the composition of the alloy nanocatalyst. Addition of a secondary oxidizer such as tert-butylhydroperoxide (TBHP) significantly enhanced the yield of the products at shorter reaction time under mild reaction conditions.