methyl 3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-6-O-benzyl-2-N-methylacetimido-2-deoxy-β-D-glucopyranoside | 862980-90-3

• 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 3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-6-O-benzyl-2-N-methylacetimido-2-deoxy-β-D-glucopyranoside
• CAS: 862980-90-3
• 化学式: C₃₁H₄₃NO₁₅
• 分子量: 669.68
• InChiKey: QLNBTBRBGDQPAH-CHPZRJSGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.84
• 重原子数：
  47.0
• 可旋转键数：
  13.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  193.17
• 氢给体数：
  1.0
• 氢受体数：
  16.0

反应信息

• 作为反应物：
  描述：

  methyl 3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-6-O-benzyl-2-N-methylacetimido-2-deoxy-β-D-glucopyranoside 在 4 A molecular sieve 、 乙酸酐 、 溶剂黄146 、 三氟甲烷磺酸甲酯 作用下， 以 乙醚 为溶剂， 反应 21.0h， 生成 methyl 2-acetamido-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-rhamnopyranosyl)-2-deoxy-α-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 O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>3)-2-acetamido-6-O-benzyl-2-deoxy-β-D-glucopyranoside 、 三氟甲烷磺酸甲酯 在 4 A molecular sieve 作用下， 以 乙醚 为溶剂， 反应 18.0h， 以76%的产率得到methyl 3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-6-O-benzyl-2-N-methylacetimido-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+