Alternative syntheses and related N.M.R. studies of precursors for internal β-d-galactopyranosyl residues in oligosaccharides, allowing chain extension at O-4
作者:Pavol Kováč、Richard B. Taylor
DOI:10.1016/0008-6215(87)80276-8
日期:1987.9
was cleaved with DCMME to give the corresponding glycosyl chloride (20). The same sequence of reactions involving 1,2,3,6-tetra-O-benzoyl-alpha-D-galactopyranose and 2,3,4,6-tetra-O-benzoyl-alpha-D-galactopyranosyl bromide afforded O-(2,3,4,6-tetra-O-benzoyl-beta-D-galactopyranosyl)-(1----4)-2,3,6-tri-O - benzoyl-alpha-D-galactopyranosyl chloride, which can be used to construct in an oligosaccharide the
由甲基2,3,6-三-O-苯甲酰基-4-O-制备2,3,6-三-O-苯甲酰基-4-O-(溴乙酰基)-α-D-吡喃半乳糖基氯(5) (溴乙酰基)-α-或-β-D-吡喃半乳糖苷通过在氯化锌存在下用二氯甲基甲基醚(DCMME)裂解而形成。5与三甲基2,3,6-三-O-苯甲酰基-β-D-吡喃半乳糖苷缩合的三氟甲磺酸银(三氟甲磺酸盐)给出相应的β-连接的二糖,将其进行O-去(溴乙酰基)化并缩合所得的二糖亲核体用5.将得到的β-连接的三糖脱保护,得到(1-4)-β-连接的D-半乳糖三糖的甲基β-糖苷。将化合物5高产率地转化为相应的1-O-β-乙酰基衍生物,将其与硫脲进行O-去(溴乙酰基)化,得到结晶的1-O-乙酰基-2,3,6-三-O-苯甲酰基-β-D-吡喃半乳糖(9)。9与5的缩合反应生成O- [2,3,6-三-O-苯甲酰基-4-O-(溴乙酰基)-β-D-吡喃半乳糖基]-(1 ---- 4)-1-O-乙酰基将-2