Differential O-3/O-4 regioselectivity in the glycosylation of alpha and beta anomers of 6-O-substituted N-dimethylmaleoyl-protected D-glucosamine acceptors.
An assessment of the relative O-3/O-4 reactivities of both methyl alpha- and beta-d-glycosides of N-dimethylmaleoyl (DMM) d-glucosamine acceptors protected at O-6 with benzoyl (Bz), benzyl (Bn), and tert-butyldiphenylsilyl (TBDPS) groups is presented using per-O-benzoylated beta-d-galactofuranosyl and per-O-acetylated alpha-d-galactopyranosyl trichloroacetimidates as glycosyl donors. Using the former donor, the alpha anomer of the 6-O-benzoylated compound gave exclusive substitution at O-3, whereas the other two compounds with alpha-configuration kept this site as preferential. The beta anomer of the 6-O-benzoylated compound gave the same amounts of reaction products on O-3 and O-4, whereas the other beta analogs carried a more reactive O-4. The same reactions were carried out using as donor the less-reactive per-O-acetylated alpha-d-galactopyranosyl trichloroacetimidate. Although the same trend was found to occur, the O-4 was always relatively more reactive with the pyranosyl donor than with the furanosyl donor, when keeping the remaining factors constant. Furthermore, the beta anomers of the acceptor gave almost exclusive substitution at O-4. These observations confirm and extend the utility of these 'matching' donor and acceptor reactivities.
Bohn
María L
ML
Instituto de Química Orgánica y de Síntesis (CONICET-UNR), Facultad de Ciencias Bioquímicas y Farmacéuticas, Suipacha 531, 2000 Rosario, Argentina.
Colombo
María I
MI
Pisano
Pablo L
PL
Stortz
Carlos A
CA
Rúveda
Edmundo A
EA
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D004187:Disaccharides / Q000737:chemistry; D004563:Electrochemistry / Q000379:methods; D005944:Glucosamine / Q000737:chemistry*; D006027:Glycosides / Q000737:chemistry; D006031:Glycosylation; D016695:Glycosyltransferases / Q000737:chemistry; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D008969:Molecular Sequence Data; D015394:Molecular Structure; D011134:Polysaccharides / Q000737:chemistry
D004187:Disaccharides; D006027:Glycosides; D011134:Polysaccharides; D016695:Glycosyltransferases; D005944:Glucosamine