methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside | 98856-39-4

• 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 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside
• 英文别名: Methyl 2-acetamido-3-O-(2,3,4,6-tetra-O-acetyl-b-D-galactopyranosyl)-4,6-O-benzylidene-2-deoxy-b-D-glucopyranoside；[(2R,3S,4S,5R,6R)-6-[[(2R,4aR,6R,7R,8R,8aS)-7-acetamido-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-yl]oxy]-3,4,5-triacetyloxyoxan-2-yl]methyl acetate
• CAS: 98856-39-4
• 化学式: C₃₀H₃₉NO₁₅
• 分子量: 653.637
• InChiKey: GSHXJRKOGNLBGH-IMSMJMBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  46
• 可旋转键数：
  14
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  190
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside 在 盐酸 、 4 A molecular sieve 、 sodium cyanoborohydride 、 N,N-二异丙基乙胺 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 methyl 2-(N-acetylacetamido)-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-6-O-benzyl-4-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  The Amide Group in N-Acetylglucosamine Glycosyl Acceptors Affects Glycosylation Outcome

  摘要：

  Glycosylation of a disaccharide containing N-acetylglucosamine with rhamnosyl and mannosyl trichloracetimidates under triethysilyl triflate catalysis led to the competitive formation of glycosyl imidates. While the rhamnosyl imidate could be rearranged to the thermodynamically favored trisaccharide, the mannosyl analogue was resistant to rearrangement. Glycosylation with perbenzylated thiorhamnosides activated with methyl triflate (MeOTf) gave the trisaccharide as well as the methyl imidate trisaccharide. The less reactive alpha-thioethyl donor led to a higher relative amount of methyl imidate trisaccharide to trisaccharide than the more reactive beta-thioglycoside. When using a more reactive thioethyl fucoside only the trisaccharide was obtained. Interestingly, the acceptor treated with MeOTf gave the N-methyl imidate that could be easily rhamnosylated and subsequently converted to the N-acetamido trisaccharide. This strategy to glycosylate O-4 of N-acetylglucosamine is under further investigation. Alternatively, bis-N-acetylation of the glucosamine prevented the formation of imidates and allowed the efficient synthesis of two Lewis A trisaccharide analogues.

  DOI：

  10.1021/jo050707+
• 作为产物：
  描述：

  methyl 2-acetylamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside 、 2,3,4,6-四乙酰氧基-alpha-D-吡喃糖溴化物 在 calcium sulfate 、 氰化汞 作用下， 以 硝基甲烷 、 苯 为溶剂， 反应 16.0h， 以84.5%的产率得到methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  乳酸-N-二糖I和N-乙酰-乳糖胺的单脱氧衍生物的合成，可作为区分α-1-岩藻糖基转移酶的底物

  摘要：

  摘要β-d -Gal-（1→3）-4-deoxy-β-d-GlcNAcOR和β-d -Gal-（1→4）-3-deoxy-β-d-GlcNAcOR的化学合成，其中报告了R =（CH2）8COOMe和Me。此外，2-deoxy-β-d-Gal-（1→3）-β-d-GlcNAcO（CH2）8COOMe和2-deoxy-β-d-Gal-（1→4）-β-d-GlcNAcO（合成CH 2）8 COOMe。关于这些化合物作为β-d-Gal-和β-d-GlcNAc-α-1-岩藻糖基转移酶的受体的行为，报道了来自其他实验室的初步结果。建议这些酶以其最有利的构象接受底物，并且该结合涉及极性和非极性相互作用，并具有在被取代的羟基附近的形貌特征。似乎取决于转移酶，识别可以包括或可以不包括两个糖单元。

  DOI：

  10.1016/0008-6215(85)85204-6

文献信息

• Synthetic Analogs of the Lewis^b-Tetrasaccharide and their Binding to Griffonia Simplicifolia Lectin-Part I
  作者：Ole Hindsgaul、Vivekanand Kamath、Joanna Sadowska、Shahul Nilar、David Bundle

  DOI：10.1055/s-2003-40329

  日期：——

  The lewis b tetrasaccharide binds specifically to the Griffonia simplicifolia lectin GS-IV. In an effort to obtain tighter binding derivatives, we have synthesized a series of analogs of this tetrasaccharide and studied their binding to the lectin. This paper (part I in a series of two) describes the synthesis of and binding studies with analogs where the galactose unit (b) has been altered at the 6-position. Even though this position does not make direct contact with the protein in the crystal structure, the binding was very sensitive to these substitutions.

  刘易斯B四糖特异性地结合到刺槐豆凝集素GS-IV上。为了获得更紧密结合的衍生物，我们合成了一系列这种四糖的类似物，并研究了它们与凝集素的结合。本文（系列中的第一部分，共两部分）描述了对半乳糖单元（b）在6位进行改变的类似物的合成及其结合研究。尽管这个位置在晶体结构中并不直接与蛋白质接触，但结合对这些取代非常敏感。
• Glycosylation of <i>N</i>-Acetylglucosamine:  Imidate Formation and Unexpected Conformation
  作者：Liang Liao、France-Isabelle Auzanneau

  DOI：10.1021/ol034669x

  日期：2003.7.1

  [GRAPHICS]Rhamnosylation in mild conditions of a disaccharide containing N-acetylglucosamine afforded the imidate 6 while at higher temperature and concentration of promoter trisaccharide 7 was isolated. The kinetic imidate 6 was independently rearranged in 50% yield to the thermodynamic trisaccharide 7. Comparative NMR studies of 7 in CDCl3 and DMSO-d(6) suggest the formation of a nonchair conformation in CDCl3. The structure of 7 was confirmed through the independent synthesis of the N-acetylacetamido trisaccharide 11.