Numata M, Sugimoto M, Shibayama S, Ogawa T
RIKEN (The Institute of Physical and Chemical Research), Saitama, Japan.
Carbohydr Res. 1988 Mar 15;174:73-85. doi: 10.1016/0008-6215(88)85082-1.
Methyl (5-acetoxyacetamido-4,7,8,9-tetra-O-acetyl-3,5- dideoxy-D-glycero-beta-D-galacto-2-nonulopyranosyl chloride)onate, prepared from N-glycolyl-neuraminic acid, was used for the glycosylation of benzyl O-(2,6-di-O-benzyl-beta-D- galactopyranosyl)-(1----4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside to give benzyl O-[methyl (5-acetoxyacetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero- alpha- and beta-D-galacto-2-nonulopyranosyl)onate]-(2----3)-O-(2,6-di-O -benzyl-beta- D-galacto-pyranosyl)-(1----4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside, and a regioisomer. Compounds 9 and 13 were converted into the corresponding glycotriaosyl glycosyl donors which, upon coupling with (2S,3R,4E)-3-O-tert-butyldiphenylsilyl-2-N- tetracosanoylsphingenine, afforded completely protected hematoside and a stereoisomer 26, respectively. Deprotection of 22 and 26 completed the first total synthesis of both hematoside and a stereoisomer, beta-NeuGc-(2----3)-beta-Gal-(1----4)-beta-Glc-(1----1)-Cer.
由N - 羟乙酰神经氨酸制备的甲基(5 - 乙酰氧基乙酰氨基 - 4,7,8,9 - 四 - O - 乙酰基 - 3,5 - 二脱氧 - D - 甘油 - β - D - 半乳糖 - 2 - 壬吡喃糖基氯)酸酯用于苄基O -(2,6 - 二 - O - 苄基 - β - D - 吡喃半乳糖基)-(1→4)-2,3,6 - 三 - O - 苄基 - β - D - 吡喃葡萄糖苷的糖基化反应，得到苄基O -[甲基(5 - 乙酰氧基乙酰氨基 - 4,7,8,9 - 四 - O - 乙酰基 - 3,5 - 二脱氧 - D - 甘油 - α - 和β - D - 半乳糖 - 2 - 壬吡喃糖基)酸酯]-(2→3)-O -(2,6 - 二 - O - 苄基 - β - D - 吡喃半乳糖基)-(1→4)-2,3,6 - 三 - O - 苄基 - β - D - 吡喃葡萄糖苷以及一种区域异构体。化合物9和13被转化为相应的糖三糖基糖基供体，它们与(2S,3R,4E)-3 - O - 叔丁基二苯基硅烷基 - 2 - N - 二十四烷酰基鞘氨醇偶联后，分别得到完全保护的血苷和一种立体异构体26。对22和26进行脱保护完成了血苷和立体异构体β - NeuGc-(2→3)-β - Gal-(α→4)-β - Glc-(α→1)-Cer的首次全合成。
