Oxidation of methyl alpha-D-glucopyranoside and some related compounds catalysed by nickel peroxide

Nickel sulphate efficiently catalyses oxidative glycol cleavage, using sodium hypochlorite as the primary oxidant. Suspended nickel peroxide is assumed to be the active intermediate. 2,3-Butanediol was oxidised (conversion 95%) to acetate at pH <10 and 20 degrees C, applying a molar ratio hypochlorite: nickel:diol of 8:0.2:1. Methyl alpha-D-glucopyranoside was initially oxidised to disodium (R)-2-O-[(R)-carboxylato(methoxy) methyl]erythrate. Subsequently oxidation to disodium (R)-2-O-[(R)-carboxylato (methoxy)methyl]glycerate took place. beta-Cyclodextrin was preferentially oxidatively cleaved (ca. 50%) between the C(2)-C(3) carbons, although oxidation at the C(6) carbon (ca. 25%) appeared to occur as well. In contrast, maltodextrin was oxidised at the primary hydroxyl functions.