Anomalous Zemplén deacylation reactions of 2-O-acyl-3-O-alkyl or -3-O-glycosyl derivatives of D-galactose and D-glucose: synthesis of O-alpha-D-mannopyranosyl-(1----4)-O-alpha-L-rhamnopyranosyl-(1----3)-D- galactose and an intermediate for the preparation of 2-O-glycosyl-3-O-(alpha-D-mannopyranosyl)-D-glucoses.
Treatment of 2-O-benzoyl (1) and 2-O-acetyl (5) derivatives of benzyl 4,6-benzylidene-3-O-(2,3,4-tri-O-acetyl-alpha-L-rhamnopyranosyl)-beta-D- galactopyranoside under Zemplén conditions (catalytic amount of sodium methoxide in methanol) gave partially deacylated disaccharides in which the 2-O-acyl groups were retained. Likewise, a similar result was obtained with the beta-L-rhamnopyranosyl analogue (3) of 1. This anomalous reaction was used in a synthesis of the title trisaccharide (17) and of methyl 4,6-O-benzylidene-3-O-(2,3:4,6-di-O-isopropylidene-alpha-D-mannopyranosy l)- alpha-D-glucopyranoside, an intermediate for the synthesis of 2-O-glycosyl-3-O-(alpha-D-mannopyranosyl)-D-glucoses.
Szurmai
Z
Z
Institute of Biochemistry, L. Kossuth University, Debrecen, Hungary.
Lipták
A
A
Snatzke
G
G
D000107:Acetylation; D002240:Carbohydrate Sequence; D055598:Chemical Phenomena; D002621:Chemistry; D000432:Methanol; D008969:Molecular Sequence Data; D014312:Trisaccharides / Q000138:chemical synthesis*
D014312:Trisaccharides; C065004:O-alpha-mannopyranosyl-(1-4)-O-alpha-rhamnopyranosyl-(1-3)-galactose; D000432:Methanol