三种含3-O-甲基-D-甘露糖的四糖的合成，作为N-糖蛋白中含木糖碳水化合物链的模型化合物。
Synthesis of three tetrasaccharides containing 3-O-methyl-D-mannose, as model compounds for xylose-containing carbohydrate chains from N-glycoproteins.
作者信息
van der Ven J G, Wijkmans J C, Kamerling J P, Vliegenthart J F
机构信息
Bijvoet Center, Department of Bio-Organic Chemistry, Utrecht University, Netherlands.
出版信息
Carbohydr Res. 1994 Feb 3;253:121-39. doi: 10.1016/0008-6215(94)80060-x.
The synthesis is reported of methyl 3,6-di-O-(3-O-methyl-alpha-D-mannopyranosyl)-2-O-beta-D-xylopyranosyl-be ta-D- mannopyranoside (2), methyl 6-O-alpha-D-mannopyranosyl-3-O-(3-O-methyl-alpha-D-mannopyranosyl)-2-O-b eta-D- xylopyranosyl-beta-D-mannopyranoside (3), and methyl 3-O-alpha-D-mannopyranosyl-6-O-(3-O-methyl-alpha-D-mannopyranosyl)-2-O-b eta-D- xylopyranosyl-beta-D-mannopyranoside (4). The various methyl beta-D-Manp acceptor derivatives were prepared from the corresponding methyl beta-D-Glcp derivatives via oxidation-reduction. All glycosyl donors were coupled using the trichloroacetimidate method at -40 degrees C in dichloromethane with trimethylsilyl triflate as a catalyst. Methyl-3-O-benzyl-4,6-O-benzylidene-beta-D-mannopyranoside (7) was condensed with 2,3,4-tri-O-acetyl-alpha-D-xylopyranosyl trichloroacetimidate (8). Regioselective reductive 4,6-O-benzylidene ring-opening on the resulting disaccharide derivative, followed by acetylation, and hydrogenation gave methyl 4-O-acetyl-2-O-(2,3,4-tri-O-acetyl-beta-D-xylopyranosyl)-beta-D-mannopyr anoside (12). Coupling of 12 with 2,4,6-tri-O-acetyl-3-O-methyl-alpha-D-mannopyranosyl trichloroacetimidate (18) afforded tetrasaccharide derivative 19, and subsequent O-deacetylation gave 2. Methyl 3-O-benzyl-4,6-O-prop-2-enylidene-beta-D-mannopyranoside (22) was condensed with 2,3,4-tri-O-acetyl-alpha-D-xylopyranosyl trichloroacetimidate (8). Regioselective reductive 4,6-O-prop-2-enylidene ring-opening on the resulting disaccharide derivative, followed by acetylation, and deallylation at O-6 gave methyl 4-O-acetyl-3-O-benzyl-2-O-(2,3,4-tri-O-acetyl-beta-D-xylopyranosyl)-beta -D- mannopyranoside (26-a), which was either condensed with 2,3,4,6-tetra-O-acetyl-alpha-D-mannopyranosyl trichloroacetimidate (27) or 18, to give trisaccharide derivatives 28 or 31, respectively. Debenzylation of 28 followed by condensation with 18 gave, after O-deacetylation, 3, whereas debenzylation of 31 followed by condensation with 27 gave, after O-deacetylation, 4.
报道了3,6 - 二 - O -（3 - O - 甲基 - α - D - 甘露吡喃糖基）- 2 - O - β - D - 木吡喃糖基 - β - D - 甘露吡喃糖苷甲酯（2）、6 - O - α - D - 甘露吡喃糖基 - 3 - O -（3 - O - 甲基 - α - D - 甘露吡喃糖基）- 2 - O - β - D - 木吡喃糖基 - β - D - 甘露吡喃糖苷甲酯（3）和3 - O - α - D - 甘露吡喃糖基 - 6 - O -（3 - O - 甲基 - α - D - 甘露吡喃糖基）- 2 - O - β - D - 木吡喃糖基 - β - D - 甘露吡喃糖苷甲酯（4）的合成。各种β - D - 甘露吡喃糖受体衍生物是通过氧化还原反应由相应的β - D - 葡糖吡喃糖衍生物制备而成。所有糖基供体均采用三氯乙酰亚胺酯法，在-40℃的二氯甲烷中，以三甲基甲硅烷基三氟甲磺酸酯为催化剂进行偶联反应。3 - O - 苄基 - 4,6 - O - 亚苄基 - β - D - 甘露吡喃糖苷甲酯（7）与2,3,4 - 三 - O - 乙酰基 - α - D - 木吡喃糖基三氯乙酰亚胺酯（8）缩合。对所得二糖衍生物进行区域选择性还原4,6 - O - 亚苄基开环反应，随后进行乙酰化和氢化反应，得到4 - O - 乙酰基 - 2 - O -（2,3,4 - 三 - O - 乙酰基 - β - D - 木吡喃糖基）- β - D - 甘露吡喃糖苷甲酯（12）。12与2,4,6 - 三 - O - 乙酰基 - 3 - O - 甲基 - α - D - 甘露吡喃糖基三氯乙酰亚胺酯（18）偶联得到四糖衍生物19，随后进行O - 脱乙酰化反应得到2。3 - O - 苄基 - 4,6 - O - 亚丙 - 2 - 烯基 - β - D - 甘露吡喃糖苷甲酯（22）与2,3,4 - 三 - O - 乙酰基 - α - D - 木吡喃糖基三氯乙酰亚胺酯（8）缩合。对所得二糖衍生物进行区域选择性还原4,6 - O - 亚丙 - 2 - 烯基开环反应，随后进行乙酰化反应，并在O - 6位进行脱烯丙基反应，得到4 - O - 乙酰基 - 3 - O - 苄基 - 2 - O -（2,3,4 - 三 - O - 乙酰基 - β - D - 木吡喃糖基）- β - D - 甘露吡喃糖苷甲酯（26 - a），其与2,3,4,6 - 四 - O - 乙酰基 - α - D - 甘露吡喃糖基三氯乙酰亚胺酯（27）或18缩合，分别得到三糖衍生物28或31。28进行脱苄基反应，随后与18缩合，经O - 脱乙酰化反应后得到3，而31进行脱苄基反应，随后与27缩合，经O - 脱乙酰化反应后得到4。
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