The synthesis of 1-thiotrehaloses and thioglycals by a directed copper-catalyzed dehydrogenative C?H thiolation the pseudo-anomeric bond glycals is described. use aminoquinoline-containing as well thiosugars or thiols coupling partners led to library thioglycosides in moderate good yields.

Natural product-like macrocycles were designed as potential antibacterial compounds. The macrocycles featured a D-glucose unit fused into a 12- or 13-member macrolactone. The rings are connected via the C6' and anomeric (C1') positions of the monosaccharide. The new macrocycles/macrolides were characterized by X-ray crystallography. Their structures showed that, in addition to the ester and alk...

Gas-phase electron-diffraction data and high-level quantum chemical calculations have been used to study the conformational behaviour of N-azidomethylpyrrolidine. The two most stable conformers with a relative abundance of about 80% at 298 K possess gauche orientation of the azidomethyl group around the C-N(pyr) bond (C-N(azido)gauche with respect to the endocyclic N(pyr)-C bond). This orientat...

The first total synthesis of dinemasone A, a bioactive metabolite with a spiroketal moiety, is described. The main strategy for the construction of the spiroketal unit involves a double intramolecular hetero-Michael addition (DIHMA) of an ynone moiety. The thus obtained axial-equatorial mono anomeric spiroketal, on spiroepimerization with ZnBr(2), was converted into the requisite axial-axial do...

In tumoral cells derived from the insulin-producing rat cell line RINm5F, both low- and high-Km glucose-phosphorylating enzymic activities were present. The hexokinase-like enzyme was inhibited by glucose 6-phosphate and displayed a greater affinity for but lower maximal velocity with alpha-D-glucose than beta-D-glucose. A comparable anomeric behavior of hexokinase was observed in breast cancer...

Abstract Based on structures determined by X-ray crystallography, ab initio MP2 calculations type A mesoionic rings give geometries in good agreement with observed values. study of four ring systems, each exocyclic oxygen, nitrogen or carbon groups, shows that the presence and configuration lone pairs significantly influences geometry configurational preference. Using a localised bond model NBO...

In this note, an hydrozirconation/bromination/Michaelis-Arbuzov sequence was developped to introduce a trimethylene phosphonate unit on ketopyranosides. Performed polyfunctional substrates bearing orthogonal protecting groups, new approach provided straightforward entry towards large diversity of glycophosphomimetics having quaternary anomeric position.