Khan S H, Jain R K, Matta K L
Department of Gynecologic Oncology, Roswell Park Memorial Institute, New York State Department of Health, Buffalo 14263.
Carbohydr Res. 1990 Oct 15;207(1):57-69. doi: 10.1016/0008-6215(90)80005-n.
Methyl 3,4,6-tri-O-benzyl-beta-D-mannopyranoside (2), methyl 2,3-O-isopropylidene-beta-D-mannopyranoside (11), and 4-nitrophenyl 2,3-O-isopropylidene-beta-D-mannopyranoside (12) were each condensed with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl bromide (1) in the presence of mercuric cyanide, to give after deprotection, methyl 2-(5) and 6-O-alpha-D-mannopyranosyl-beta-D-mannopyranoside (15), and 4-nitrophenyl 6-O-alpha-D-mannopyranosyl-beta-D-mannopyranoside (20), respectively. A similar condensation of 11 with 3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-a lpha-D- mannopyranosyl bromide (21) and 2,3,4-tri-O-acetyl-6-O-(2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl)-a lpha D-mannopyranosyl bromide (25), followed by removal of protecting groups, afforded methyl O-alpha-D-mannopyranosyl-(1----2)-O-alpha-D-mannopyranosyl-(1----6)-beta -D- mannopyranoside (24) and methyl O-alpha-D-mannopyranosyl-(1----6)-O-alpha-D-mannopyranosyl-(1----6)-beta -D- mannopyranoside (28), respectively. Bromide 25 was also condensed with 12 to give a trisaccharide derivative which was deprotected to furnish 4-nitrophenyl O-alpha-D-mannopyranosyl-(1----6)-alpha-D-mannopyranosyl-(1----6)-beta-D - mannopyranoside (31). Phosphorylation of methyl 3,4,6-tri-O-benzyl-2-O-alpha-D-mannopyranosyl-beta-D-mannopyranoside and 15 with diphenyl phosphorochloridate in pyridine gave the 6'-phosphates 6 and 16, respectively. Hydrogenolysis of the benzyl and phenyl groups provided methyl 2-O-(disodium alpha-D-mannopyranosyl 6-phosphate)-beta-D-mannopyranoside (7) and methyl 6-O-(disodium alpha-D-mannopyranosyl 6-phosphate)-beta-D-mannopyranoside (17) after treatment with Amberlite IR-120 (Na+) cation-exchange resin. The structures of compounds 5, 7, 15, 17, 20, 24, 28, and 31 were established by 13C-n.m.r. spectroscopy.
3,4,6-三-O-苄基-β-D-甘露吡喃糖苷（2）、2,3-O-异亚丙基-β-D-甘露吡喃糖苷（11）和4-硝基苯基2,3-O-异亚丙基-β-D-甘露吡喃糖苷（12）分别在氰化汞存在下与2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基溴（1）缩合，脱保护后分别得到2-（5）和6-O-α-D-甘露吡喃糖基-β-D-甘露吡喃糖苷（15）以及4-硝基苯基6-O-α-D-甘露吡喃糖基-β-D-甘露吡喃糖苷（20）。11与3,4,6-三-O-乙酰基-2-O-（2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基）-α-D-甘露吡喃糖基溴（21）和2,3,4-三-O-乙酰基-6-O-（2,3,4,6-四-O-乙酰基-α-D-甘露吡喃糖基）-α-D-甘露吡喃糖基溴（25）进行类似缩合，然后除去保护基，分别得到O-α-D-甘露吡喃糖基-（1→2）-O-α-D-甘露吡喃糖基-（1→6）-β-D-甘露吡喃糖苷（24）和O-α-D-甘露吡喃糖基-（1→6）-O-α-D-甘露吡喃糖基-（1→6）-β-D-甘露吡喃糖苷（28）。溴化物25也与12缩合得到一种三糖衍生物，脱保护后得到4-硝基苯基O-α-D-甘露吡喃糖基-（1→6）-α-D-甘露吡喃糖基-（1→6）-β-D-甘露吡喃糖苷（31）。3,4,6-三-O-苄基-2-O-α-D-甘露吡喃糖基-β-D-甘露吡喃糖苷和15在吡啶中用二苯基磷酰氯进行磷酸化反应，分别得到6'-磷酸酯6和16。苄基和苯基经氢解后，用Amberlite IR-120（Na+）阳离子交换树脂处理，得到2-O-（α-D-甘露吡喃糖基6-磷酸二钠盐）-β-D-甘露吡喃糖苷（7）和6-O-（α-D-甘露吡喃糖基6-磷酸二钠盐）-β-D-甘露吡喃糖苷（17）。化合物5、7、15、17、20、24、28和31的结构通过13C核磁共振光谱确定。
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