Study of interhalogens/silver trifluoromethanesulfonate as promoter systems for high-yielding sialylations.
We have studied interhalogen/silver trifluoromethanesulfonate (IX/AgOTf) promoted glycosylations and found differences in the sensitivity of the formed oxocarbenium ions (e.g. from compounds with or without participating groups) toward halide nucleophiles. These differences can be explained using the HSAB theory. By applying this theory on sialylations, we increased the yield for a model reaction from a highly unpredictable 35-46% using ICl to 74% using IBr. We have also showed that the most prominent role of the silver ions is lowering the concentration of the halide nucleophile rather than activating the interhalogen compound and, by increasing the amount of AgOTf from 1 to 1.5 equiv (with respect to IBr), the yield in the model reaction improved from 74% to 89%. A comparison of two different anomeric leaving groups showed that glycal formation can be minimized using a thiophenyl donor instead of xanthate. By combining these observations, we were able to increase the yield of the model reaction to 97%.
Meijer
Andréas
A
Organic and Bioorganic Chemistry, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden.
Ellervik
Ulf
U
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000138:chemical synthesis* / Q000737:chemistry; D006031:Glycosylation; D007202:Indicators and Reagents; D008698:Mesylates / Q000737:chemistry*; D008958:Models, Molecular; D008969:Molecular Sequence Data; D012794:Sialic Acids / Q000737:chemistry*; D013053:Spectrophotometry; D014312:Trisaccharides / Q000138:chemical synthesis / Q000737:chemistry
D004187:Disaccharides; D007202:Indicators and Reagents; D008698:Mesylates; D012794:Sialic Acids; D014312:Trisaccharides; C012077:trifluoromethanesulfonic acid