Sugar fragmentation in the Maillard reaction cascade:: Formation of short-chain carboxylic acids by a new oxidative α-dicarbonyl cleavage pathway

The formation of short-chain carboxylic acids was studied in Maillard model systems ( 90 C, pH 6-10) with emphasis on the role of oxygen and water. The total amount of acetic acid formed did not depend on the reaction atmosphere. In the presence of labeled dioxygen or water (O-18(2), (H2O)-O-17), labeled oxygen was partially incorporated into acetic acid. Thermal treatment of 1-deoxy-D-erythro2,3-hexodiulose (1) and 3-deoxy-D-erythro-hexos-2-ulose in the presence of O-17-enriched water under alkaline conditions led to acetic and formic acid, respectively, as indicated by O-17 NMR spectroscopy. The suggested mechanism involves an oxidative alpha-dicarbonyl cleavage leading to an intermediary mixed acid anhydride that releases the acids, e. g., acetic and erythronic acid, from 1. Similarly, glyceric and lactic acids were formed from 1-deoxy-3,4-hexodiuloses, corroborated by complementary analytical techniques. This paper provides for the first time evidence for the direct formation of acids from C6-alpha-dicarbonyls by an oxidative mechanism and incorporation of a (OH)-O-17 group into the carboxylic moiety. The experimental data obtained support the coexistence of at least two newly described reaction mechanisms leading to carboxylic acids, i.e., (i) a hydrolytic,alpha-dicarbonyl cleavage as a major pathway and (ii) an alternative minor pathway via oxidative beta-dicarbonyl cleavage induced by oxidizing species.