Concentration Dependence of Glycosylation Outcome: A Clue to Reproducibility and Understanding the Reasons Behind

• Published in: European journal of organic chemistry Vol. 2012; no. 10; pp. 1926 - 1934
• Main Authors: Kononov, Leonid O., Malysheva, Nelly N., Orlova, Anna V., Zinin, Alexander I., Laptinskaya, Tatiana V., Kononova, Elena G., Kolotyrkina, Natalya G.
• Format: Journal Article
• Language: English; Russian
• Published: Weinheim WILEY-VCH Verlag 01.04.2012; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Aggregation; Chemistry; Chemistry, Organic; Glycosylation; Physical Sciences; Science & Technology; Sialic acids; Stereoselectivity; GLYCOSIDE; ONE-POT SYNTHESIS; DONOR; SIALYLATION; OPTICAL-ROTATION; Glycosylation; SIALIC-ACID; Sialic acids; Stereoselectivity; Aggregation; NEURAMINIC ACID; STEREOSELECTIVE GLYCOSYLATION; 1ST EXAMPLE; EFFICIENT
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201101613

Changes in the concentration of reagents (0.009–0.2 M) have been shown to dramatically effect the yield and stereoselectivity of glycosylation with a sialic acid based glycosyl donor in a complex nonlinear manner that correlates with changes in the structures of the supramers of the reagents. The yield of disaccharide gradually increases with concentration and levels off at concentrations of glycosyl donor higher than 69 mM. The ratio of anomers is very high at some concentrations (α/β ≈ 20:1), moderate (α/β ≈ 8:1) or very low (α/β ≈ 4:1) at others. The formation of mixed supramers of glycosyl donor and glycosyl acceptor at concentrations exceeding 69 mM was detected by polarimetry and laser light scattering. Depending on the concentration, the reagents can form different supramers with distinct chemical properties. The changes in supramer structure (indicated by the red vertical arrows) correlate with the glycosylation yield (1) and stereoselectivity (2) and can be detected by physical methods.