•A regio-controlled one-pot synthesis of 2-deoxy-2-sulfonamino-1-O-glycosides from acetylated glycals.•1,2:2,3-Di-trans-substituted glycosides were formed in a stereospecific manner.•This amidoglycosylation was applied to a variety of primary and secondary alcohols.•The reaction would proceed via rhodium(II)-catalyzed intermolecular aziridination with a sulfonyl-nitrene.A regio- and stereo-controlled, rhodium(II)-catalyzed amidoglycosylation of alcohols has been developed using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglycosylation was applied to a variety of primary and secondary alcohols to afford the β-O-glycosides with acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination of the glycal from the α-face followed by SN2 reaction with alcohol at C-1 from the β-face to give 1,2:2,3-di-trans-substituted isomer only.

A regio- and stereo-controlled, one-pot amidoglycosylation of alcohols has been achieved using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene in the presence of a rhodium(II) catalyst. The reaction would proceed via stereoselective intermolecular aziridination of the glycal.

•Synthesis of all four stereoisomers of 5-formyl-4-hydroxymethyl-1,3-oxazolidin-2-ones.•Regioselective cyclization of N-phenoxycarbonyl-d-glucosamine to the 2-N,3-O-carbonyl-derivative.•2-N,3-O-Carbonyl-d-glucosamine could epimerize to d-mannosamine derivative.•4,5-cis-5-Formyl-4-hydroxymethyl-oxazolidones form five-membered lactol ring.•4,5-trans-5-Formyl-4-hydroxymethyl-oxazolidones mainly form methanol adduct of the aldehyde.All four stereoisomers of 5-formyl-4-hydroxymethyl-1,3-oxazolidin-2-ones (FHOs) were conveniently prepared from d-glucosamine by base-catalyzed epimerizations. 2-N,3-O-Carbonyl-d-glucosamine (7) was successively treated with NaBH4 and NaIO4 to give (4S,5R)-FHO 18, which was epimerized with DBU in DMF to give (4S,5S)-FHO 20. The glucosamine derivative 7 was epimerized to 2-N,3-O-carbonyl-d-mannosamine 23, from which (4R,5R)- and (4R,5S)-FHO derivatives (27 and 31) were prepared. The NMR measurements revealed that the 4,5-cis-4(or 5)-formyl-5(or 4)-hydroxymethyl-oxazolidinone derivatives form five-membered lactol ring, whereas the 4,5-trans-disubstituted derivatives form the hydrate or methanol adduct of the open-chain aldehyde, or the symmetrical dimer.