Abstract
Treatment of the osone (aldos-2-ulose), d-[1-13C]glucosone (1 1), with sodium molybdate at 90° for 30 h gave a mixture of d-[2-13C]gluconate (2 2) and d-[2-13C]mannonate (3 2) in an 85:15 ratio, indicating that the reaction proceeds with C1-C2 transposition similar to that observed previously with aldoses. Reactions with several singly and doubly 13C-labeled isotopomers of 1 confirmed this transposition. In contrast to the aldose reaction, the reaction with 1 is irreversible, presumably due to electrostatic repulsion between the negatively charged catalytically active bimolybdate species and the negatively charged aldonate product. The production of 2 and 3 is mediated by the formation of two structurally distinct bimolybdate complexes, one producing the gluco isomer and the other producing the manno isomer. Reaction byproducts were also observed, specifically d-[1-13C]arabinose (4 1) and [13C]formate (5), when 1 1 was used as the reactant. These byproducts appear to form from the breakdown of bimolybdate complexes via alternative pathways that compete with those responsible for aldonate formation.
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