Bausteine von Oligosacchariden, XXXIX. Synthese der Glycopeptide β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Ser und β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Thr

6-O-Acetyl-2-azido-4-O-benzyl-2-desoxy-3-O-trichloracetyl-β-D-glucopyranosylchlorid (2) last sich in Dichlormethan/Toluol bei Gegenwart von Silbercarbonat/Silberperchlorat mit dem Serin-derivat 3 und dem Threoninderivat 7 selektiv zu den α-Glycosiden 5 und 9 umsetzen. In einer entsprechenden Reaktion kann das β-Pyranosylchlorid des 2-Azido-2-desoxylactose-Derivates 12 mit 3 und 7 zu den Disaccharid-Glycosiden 13 und 14 umgesetzt werden. Beide Reaktionen lassen sich ebenfalls stereoselektiv nur zum α-Glycosid lenken. Durch vollstandige Entblockierung von 13 und 14 sind die beiden Glycopeptide β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Ser (17) und β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Thr (20) zu erhalten. Building Units of Oligosaccharides, XXXIX1). — Synthesis of the Glycopeptides β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Ser and β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Thr In the presence of silver carbonate/silver perchlorate and dichloromethane/toluene as solvent 6-O-acetyl-2-azido-2-deoxy-3-O-trichloroacetyl-β-D-glucopyranosyl chloride (2) provides the α-glycosides 5 and 9 with derivatives of L-serine and L-threonine (3 and 7) with high stereoselectivity. Corresponding to this reaction the β-chloride of 2-azido-2-deoxylactose derivative 12 can be converted into disaccharide glycosides 13 and 14 with 3 or 7, respectively. Likewise, both reactions only yield α-glycosides stereoselectively. Removal of the protective groups from 13 and 14 results in the glycopeptides β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Ser (17) and β-D-Gal(1 4)-α-D-GlcNAc(1 O)-L-Thr (20).

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