Prevalence of Oxetanose Forms in the Tautomeric Equilibrium of β-Hydroxy-1,5-dicarbonyl Monosaccharides

The synthesis of 4-deoxy- and 4-deoxy-4-C-methylhexos-5-uloses, starting from 4-deoxyhex-4-enopyranosides, and a nuclear magnetic resonance (NMR) study of their isomeric composition are reported. The NMR spectra show that the two delta-dicarbonyl sugars exist as two anomeric alpha- and beta-oxetanosyl forms, derived from the hemiacetalization of the C-3 equilibria hydroxyl group with the aldehydic carbon. The observed tautomeric have been rationalized with computational calculations. Interestingly, this is the first time that dicarbonyl derivatives are mostly present in their oxetanose forms, offering a new entry into this very interesting type of scaffold.