Side Chain Conformation and Its Influence on Glycosylation Selectivity in Hexo- and Higher Carbon Furanosides.

We describe the synthesis and side chain conformational analysis of a series of four 6-deoxy-2,3,5-tri-O-benzyl hexofuranosyl donors with the d-gluco, l-ido, d-altro, and l-galacto configurations. The conformation of the exocyclic bond of these compounds depends on the relative configuration of the point of attachment of the side chain to the ring and of the two flanking centers and can be predicted on that basis analogously to the heptopyranose analogs. Variable-temperature nuclear magnetic resonance (VT NMR) spectroscopy of the activated donors reveals complex, configuration-dependent mixtures of intermediates that we interpret in terms of fused and bridged oxonium ions arising from participation by the various benzyl ethers. The increased importance of ether participation in the furanoside series compared to the pyranosides is discussed in terms of the reduced stabilization afforded to furanosyl oxocarbenium ions by covalent triflate formation. The stereoselectivities of the four donors are discussed on the basis of the benzyl ether participation model.

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.