methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-β-D-galactopyranoside | 168139-49-9

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-β-D-galactopyranoside
• 英文别名: [(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-[(2R,3R,4R,5R,6S)-3-acetyloxy-2-(acetyloxymethyl)-5-(1,3-dioxoisoindol-2-yl)-6-methylsulfanyloxan-4-yl]oxyoxan-2-yl]methyl acetate
• CAS: 168139-49-9
• 化学式: C₃₃H₃₉NO₁₇S
• 分子量: 753.735
• InChiKey: IJHFJUTVGOPKSR-PZJMFALOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  52.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  222.87
• 氢给体数：
  0.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-<2,3,6-tri-O-benzyl-4-O-(2,4,6-tri-O-benzyl-α-D-galactopyranosyl)-β-D-galactopyranosyl>-β-D-glucopyranoside 、 methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-β-D-galactopyranoside 在 N-碘代丁二酰亚胺 、 molecular sieve 、 三氟甲磺酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 1.0h， 以87%的产率得到2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2,3,6-tri-O-benzyl-4-O-<2,4,6-tri-O-benzyl-3-O-<4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-galactopyranosyl>-α-D-galactopyranosyl>-β-D-galactopyranosyl)
  参考文献：
  名称：

  Synthesis of the saccharide moiety of galactosylgloboside (SSEA-3) and its conjugation to bovine serum albumin and sepharose

  摘要：

  The pentasaccharide glycoside corresponding to galactosylgloboside (SSEA-3), beta-D-Gal p-(1 --> 3)-beta-D-Gal pNAc-(1 --> 3)-alpha-D-Gal p-(1 --> 4)-beta-D-Gal p-(1 --> 4)-beta-D-Glc p-1-OCH2CH2Si-(CH3)(3) (4), was synthesized via glycosylation (87%) of 2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-[2,3 ,6-tri-O-benzyl-4-O-(2,4,6-tri-O-benzyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside (2) with the glycosyl donor methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)- 1-thio-beta-D-galactopyranoside (1), followed by removal of protecting groups. Compound 4 was transformed into the spacer glycoside beta-D-Gal p-(1 --> 3)-beta-D-Gal pNAc-(1 --> 3)-alpha-D-Gal p-(1 --> 4)-beta-D-Gal p-(1 --> 4)-beta-D-Glc p-1-SCH2CH2COOH (10), which was coupled to bovine serum albumin (BSA), and Sepharose beads, to give the corresponding neoglycoprotein (11, 6 mol of saccharide/mol of BSA) and glycosylated Sepharose (12, 2.7 mu mol of saccharide/mL of sedimented beads), respectively. An improved synthesis of a protected globotetraoside beta-D-Gal pNAc-(1 --> 3)-alpha-D-Gal p-(1 --> 4)-beta-D-Gal p-(1 --> 4)-beta-D-Glc p-1-OCH(2)CH(2)SiMe(3) is also reported.

  DOI：

  10.1016/0008-6215(95)00044-t
• 作为产物：
  描述：

  2-(trimethylsilyl)ethyl 4,6-di-O-acetyl-2-azido-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-galactopyranoside 在 吡啶 、 sodium tetrahydroborate 、 三氟甲磺酸三甲基硅酯 、 三氟化硼乙醚 、 硼酸 、 nickel dichloride 作用下， 以 二氯甲烷 为溶剂， 反应 79.66h， 生成 methyl 4,6-di-O-acetyl-2-deoxy-2-phthalimido-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  适于引入β-d-Galp-（1→3）-α-和-β-d-GalpNAc基团的二糖糖基供体的合成

  摘要：

  将2-（三甲基甲硅烷基）乙基2-叠氮基-4,6-O-亚苄基-2-脱氧-β-d-吡喃半乳糖苷（4）与苯基2,3,4,6-四-O-乙酰基-1-糖基化硫代-β-d-吡喃半乳糖苷得到2-（三甲基甲硅烷基）乙基2-叠氮基-4,6-O-亚苄基-2-脱氧-3-O-（2,3,4,6-四-O-乙酰基- β-d-吡喃半乳糖苷）-β-d-吡喃半乳糖苷（6），产率为99％。除去亚苄基和乙酰化得到关键中间体2-（三甲基甲硅烷基）乙基4，6-二-O-乙酰基-2-叠氮基-2-脱氧-3-O-（2,3,4,6-四- O-乙酰基-β-d-吡喃半乳糖基）-β-d-吡喃半乳糖基）（7），将其转化为甲基4,6-二-O-乙酰基-2-脱氧-2-邻苯二甲酰亚胺基-3-O-（2分两个步骤制备（3,4,6-四-O-乙酰基-β-d-吡喃半乳糖苷）-1-硫代-β-d-吡喃半乳糖苷（9），总产率为69％。同样地，将7分两步转化为4,6-二-O-乙

  DOI：

  10.1016/0008-6215(95)00026-p

文献信息

• Synthesis of Ganglioside Lactams Corresponding to GM1-, GM2-, GM3-, and GM4-Ganglioside Lactones
  作者：Michael Wilstermann、Leonid O. Kononov、Ulf Nilsson、Asim K. Ray、Goeran Magnusson

  DOI：10.1021/ja00122a002

  日期：1995.5

  Ganglioside lactams are potentially useful analogs of ganglioside lactones, which are highly immunogenic derivatives of gangliosides. The lactam corresponding to the G(M3)-lactone saccharide has been synthesized by sialylation of a suitably protected lactose derivative carrying an azido group in the 2'-position, followed by reduction and ring closure to form G(M3)-lactam. Glycosylation in the 4-position of the central saccharide unit gave the G(M2)- and G(M1)- lactam saccharides. By a similar route, a 2-azido-Gal derivative was sialylated and treated as above to give the G(M4)-lactam saccharide. Deprotection gave the G(M2-4)-lactam saccharides in water soluble form, whereas attempted deprotection of the G(M1)-lactam caused its degradation. The G(M3)-lactam saccharide was coupled to ceramide, to afford the ganglioside lactam analog, and via a spacer to bovine serum albumin (BSA). The BSA conjugate was used as immunogen to raise monoclonal antibodies that cross-reacted with G(M3)-lactone. The antibodies were used in a histological staining of murine melanoma cells, clearly showing the presence of G(M3)-lactone on the cell surface. Keeping the G(M2-4)-lactam saccharides in D2O at 37 degrees C for 1 month caused marginal (0-11%) hydrolysis of the lactam ring.