An efficient short-step total synthesis of ganglioside GM3: effective usage of the neighbouring group participation strategy.
We have developed an efficient methodology for highly stereoselective sialylation using 3-position substituted sialic acids and have prepared 2a having a 3 beta-phenylthio group as a sialic donor. Glycosylation of suitably protected lactoside 3 with 2a gave only the alpha-sialyl trisaccharide 16 in good yield. Condensation of the azidosphingosine 4 with the acetate 17 using promotors, DMTST or NIS-TfOH, afforded the glycolipid 18, which was directly transformed to 20 by reduction with Bu3P and subsequent acylation with octadecanoic acid in the presence of WSC. Removal of the protecting groups generated ganglioside GM3 (1).
Tomoo
T
T
Laboratory of Organic Chemistry, School of Agriculture, Nagoya University, Japan.
Kondo
T
T
Abe
H
H
Tsukamoto
S
S
Isobe
M
M
Goto
T
T
D002240:Carbohydrate Sequence; D005679:G(M3) Ganglioside / Q000138:chemical synthesis*; D006031:Glycosylation; D008968:Molecular Conformation; D008969:Molecular Sequence Data; D019158:N-Acetylneuraminic Acid; D012794:Sialic Acids / Q000737:chemistry*
D005679:G(M3) Ganglioside; D012794:Sialic Acids; D019158:N-Acetylneuraminic Acid