Synthesis of 3'- and 4'-deoxyfluorolactose and its Me3SiCH2CH2 and ceramide derivatives.
(2-Trimethylsilyl)ethyl (Me3SiCH2CH2)3'- and 4'-deoxyfluorolactosides (1 and 3) were synthesized by glycosylation of Me3SiCH2CH2 2,3,6-tri-O-benzyl-beta-D-glucopyranoside with 2,4,6-tri-O-acetyl-3-deoxy-3-fluoro-beta-D-galactopyranosyl bromide and 2,3,6-tri-O-benzyl-4-deoxy-4-fluoro-beta-D-galactopyranosyl bromide. Anomeric deblocking of the fully acetyled Me3SiCH2CH2 glycosides (12 and 13) gave the corresponding hemiacetals 14 and 15. Removal of the acetyl groups gave 3'- and 4'-deoxyfluorolactose (2 and 4). The deoxyfluorolactosylceramides 5 and 6 were synthesized via boron trifluoride etherate- or silver triflate-activation of the trichloroacetimidates prepared from 14 and 15. Silver triflate-mediated glycosylations showed lower reaction rates, and fewer byproducts were formed.
Ekberg
T
T
Chemical Center, Lund Institute of Technology, University of Lund, Sweden.
Magnusson
G
G
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002518:Ceramides; D007202:Indicators and Reagents; D007785:Lactose / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008969:Molecular Sequence Data; D009904:Optical Rotation; D013329:Structure-Activity Relationship; D014297:Trimethylsilyl Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D002518:Ceramides; D007202:Indicators and Reagents; D014297:Trimethylsilyl Compounds; D007785:Lactose