Syntheses of Legionaminic Acid, Pseudaminic Acid, Acetaminic Acid, 8-epi-Acetaminic Acid, and 8-epi-Legionaminic Acid Glycosyl Donors from N-Acetylneuraminic Acid by Side Chain Exchange.

Metaperiodate cleavage of the glycerol side chain from an N-acetyl neuraminic acid-derived thioglycoside and condensation with the two enantiomers of the Ellman sulfinamide afford two diastereomeric N-sulfinylimines from which bacterial sialic acid donors with the legionaminic and acetaminic acid configurations and their 8-epi-isomers are obtained by samarium iodide-mediated coupling with acetaldehyde and subsequent manipulations. A variation on the theme, with inversion of the configuration at C5, similarly provides two differentially protected pseudaminic acid donors.