title: Prevalence of oxetanose forms in the tautomeric equilibrium of β-hydroxy-1,5-dicarbonyl monosaccharides.
abstract: 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 δ-dicarbonyl sugars exist as two anomeric α- and β-oxetanosyl forms, derived from the hemiacetalization of the C-3 hydroxyl group with the aldehydic carbon. The observed tautomeric equilibria 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.
authors.affiliation: Università di Catania , Dipartimento di Scienze del Farmaco, viale A. Doria 6, I-95125 Catania, Italy.
authors.forename: Venerando
authors.initials: V
authors.lastname: Pistarà
authors.forename: Antonino
authors.initials: A
authors.lastname: Corsaro
authors.forename: Antonio
authors.initials: A
authors.lastname: Rescifina
authors.forename: Giorgio
authors.initials: G
authors.lastname: Catelani
authors.forename: Felicia
authors.initials: F
authors.lastname: D'Andrea
authors.forename: Lorenzo
authors.initials: L
authors.lastname: Guazzelli
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D005663:Furans / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009005:Monosaccharides / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D005663:Furans; D009005:Monosaccharides