SYNTHESIS OF DISACCHARIDE GLYCOSYL DONORS SUITABLE FOR INTRODUCTION OF THE BETA-D-GAL P-(1-]3)-ALPHA- AND -BETA-D-GAL PNAC GROUPS
SYNTHESIS OF DISACCHARIDE GLYCOSYL DONORS SUITABLE FOR INTRODUCTION OF THE BETA-D-GAL P-(1-]3)-ALPHA- AND -BETA-D-GAL PNAC GROUPS
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DOI：
10.1016/0008-6215(95)00026-p
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发表时间：
1995-07-21
影响因子：
3.1
通讯作者：
MAGNUSSON, G
中科院分区：
文献类型：
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作者：
WILSTERMANN, M;MAGNUSSON, G
2-（三甲基硅基）乙基2-叠氮基-4，6-O-亚苄基-2-脱氧-β-D-吡喃半乳糖苷（4）与苯基2，3，4，6-四-O-乙酰基-1-硫代-β-D-吡喃半乳糖苷进行糖基化反应，得到2-（三甲基硅基）乙基2-叠氮基-4，6-O-亚苄基-2-脱氧-3-O-（2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖基）-β-D-吡喃半乳糖苷（6），收率99%。除去亚苄基并乙酰化得到关键中间体2-（三甲基硅烷基）乙基4，6-二-O-乙酰基-2-叠氮基-2-脱氧-3-O-（2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖基）-β-D-吡喃半乳糖苷（7），将其转化为甲基4，6-二-O-乙酰基-2-脱氧-2-邻苯二甲酰亚氨基-3-O-（2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖基）-1-硫代-β-D-吡喃半乳糖苷（9），总收率为69%。类似地，以86%的总收率将7分两步转化为4，6-二-O-乙酰基-2-叠氮基-2-脱氧-3-O-（2，3，4，6-四-O-乙酰基-β-D-吡喃半乳糖基）-α-D-吡喃半乳糖基溴（11）。化合物9和11是用于引入β-D-Gal p-（1 -> 3）-β-和-α-D-Gal pNAc基团的合适的糖基供体。
2-(Trimethylsilyl)ethyl 2-azido-4,6-O-benzylidene-2-deoxy-beta-D-galactopyranoside (4) was glycosylated with phenyl 2,3,4,6-tetra-O-acetyl-1-thio-beta-D-galactopyranoside to give 2-(trimethylsilyl)ethyl 2-azido-4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-beta-D-galactopyranoside (6) in 99% yield. Removal of the benzylidene group and acetylation gave the key intermediate 2-(trimethylsilyl)ethyl 4,6-di-O-acetyl-2-azido-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-beta-D-galactopyranoside (7), which was transformed into methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-1-thio-beta-D-galactopyranoside (9) in two steps in an overall yield of 69%. Similarly, 7 was transformed in two steps into 4,6-di-O-acetyl-2-azido-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-alpha-D-galactopyranosyl bromide (11) in an over-all yield of 86%. Compounds 9 and 11 are suitable glycosyl donors for introduction of the beta-D-Gal p-(1 --> 3)-beta- and -alpha-D-Gal pNAc groups.