Jain R K, Piskorz C F, Matta K L
Department of Gynecologic Oncology, Roswell Park Cancer Institute, Buffalo, NY 14263, USA.
Carbohydr Res. 1995 Oct 2;275(2):231-43. doi: 10.1016/0008-6215(95)00162-m.
Allyl 2-acetamido-4,6-O-(4-methoxybenzylidene)-2-deoxy-alpha-D-galact opy ranoside (1) was condensed with either 2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl bromide (2) or 2,3,4-tri-O-benzoyl-6-O-bromoacetyl-alpha-D-galactopyranosyl bromide (14) in the presence of mercuric cyanide. Selective substitution with methyl, sulfo or both at desired positions, followed by the removal of protecting groups, afforded allyl O-(beta-D-galactopyranosyl)-(1-->3)-2-acetamido-2-deoxy-6-O-methyl-alpha -D- galactopyranoside (5), allyl O-(6-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy-6- O-methyl-alpha-D-galactopyranoside (10), allyl O-(beta-D-galactopyranosyl)-(1-->3)-2-acetamido-2-deoxy-6-O-sulfo-alpha- D- galactopyranoside sodium salt (13), allyl O-(6-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy- alpha-D-galactopyranoside (17) and allyl O-(3-O-sulfo-beta-D-galactopyranosyl sodium salt)-(1-->3)-2-acetamido-2-deoxy- alpha-D-galactopyranoside (22). The structures of compounds 5, 10, 13, 17 and 22 were established by 13C NMR and FAB mass spectroscopy.
烯丙基 2-乙酰氨基-4,6-O-(4-甲氧基亚苄基)-2-脱氧-α-D-吡喃半乳糖苷(1)在氰化汞存在下与 2,3,4,6-四-O-乙酰基-α-D-吡喃半乳糖基溴(2)或 2,3,4-三-O-苯甲酰基-6-O-溴乙酰基-α-D-吡喃半乳糖基溴(14)缩合。在所需位置进行甲基、磺基或两者的选择性取代，然后除去保护基团，得到烯丙基 O-(β-D-吡喃半乳糖基)-(1→3)-2-乙酰氨基-2-脱氧-6-O-甲基-α-D-吡喃半乳糖苷(5)、烯丙基 O-(6-O-磺基-β-D-吡喃半乳糖基钠盐)-(1→3)-2-乙酰氨基-2-脱氧-6-O-甲基-α-D-吡喃半乳糖苷(10)、烯丙基 O-(β-D-吡喃半乳糖基)-(1→3)-2-乙酰氨基-2-脱氧-6-O-磺基-α-D-吡喃半乳糖苷钠盐(13)、烯丙基 O-(6-O-磺基-β-D-吡喃半乳糖基钠盐)-(1→3)-2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖苷(17)和烯丙基 O-(3-O-磺基-β-D-吡喃半乳糖基钠盐)-(1→3)-2-乙酰氨基-2-脱氧-α-D-吡喃半乳糖苷(22)。化合物 5、10、13、17 和 22 的结构通过 13C NMR 和 FAB 质谱确定。
