Abstract The synthesis and characterisation of α-oxo aldehyde-supported silicas by the sol- gel procedure is described. The glyoxylyl group was generated after gelation, either by periodic oxidation of gluconamide chains or by deprotection of a diisopropylthioacetal- protected derivative. The accessibility and reactivity of the supported α-oxo aldehyde function was investigated in model reactions with hydroxylamine and hydrazine ...