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Pseudaminic acid is an amino deoxy sialic acid whose glycosides are essential components of many pathogenic Gram-negative bacterial cell walls including those from Pseudomonas aeruginosa, Vibrio cholerae, Campylobacter jejuni, Campylobacter coli, Vibrio vulnificus, and Pseudoalteromonas distincta. The study of pseudaminic acid glycosides is however hampered by poor availability from nature and the paucity of good synthetic methods and limited to no understanding of the factors controlling stereoselectivity. Conformational analysis of the side chains of various stereoisomeric sialic acids suggested that the side chain of pseudaminic acid would take up the most electron-withdrawing trans, gauche-conformation, as opposed to the gauche, gauche conformation of N-acetyl neuraminic acid and the gauche, trans-conformtion of 7- epi N-acetyl neuraminic acid, leading to the prediction of high equatorial selectivity. This prediction is borne out by the synthesis of a suitably protected pseudaminic acid donor from N-acetyl neuraminic acid in 20 steps and 5% overall yield and by the exquisite equatorial selectivity it displays in coupling reactions with typical glycosyl acceptors. The selectivity of the glycosylation reactions is further buttressed by the development and implementation of conditions for the regioselective release of the two amines from the corresponding azides, such as required for the preparation of the lipopolysaccharides. These findings open the way to the synthesis and study of pseudaminic acid-based bacterial lipopolysaccharides and, importantly in the broader context of glycosylation reactions in general, underline the significant role played by side-chain conformation in the control of reactivity and selectivity.

journal of the american chemical society

Synthesis and Stereocontrolled Equatorially Selective Glycosylation Reactions of a Pseudaminic Acid Donor: Importance of the Side-Chain Conformation and Regioselective Reduction of Azide Protecting Groups