1-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl)-2-propene | 257933-03-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl)-2-propene
• 英文别名: [(2R,3R,4S,5S,6R)-4,5-diacetyloxy-3-[(2S,3R,4S,5S,6R)-3,4-diacetyloxy-6-(acetyloxymethyl)-5-[(2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxan-2-yl]oxy-6-prop-2-enyloxan-2-yl]methyl acetate
• CAS: 257933-03-2
• 化学式: C₆₁H₇₂O₂₁
• 分子量: 1141.23
• InChiKey: AIRMMYFLYSTKLO-HOSJONCDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.8
• 重原子数：
  82
• 可旋转键数：
  33
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  241
• 氢给体数：
  0
• 氢受体数：
  21

反应信息

• 作为反应物：
  描述：

  1-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl)-2-propene 在 碳酸氢钠 、 臭氧 、 四甲基胍 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 19.0h， 生成 2-(trimethylsilyl)ethyl 4-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl)-2-(tert-butyloxycarbonylamino)-2-butenoate
  参考文献：
  名称：

  Synthesis of α- and β-Carbon-Linked Serine Analogues of the P^k Trisaccharide

  摘要：

  The synthesis of glycopeptide ligands for a range of biomedically relevant carbohydrate -binding proteins is a topic of great importance to the glycobiology community. This task is impeded by the inherent instability of glycosyl linkages to serine/threonine, the normal sites of O-glycosylation in proteins. We have previously developed methodology for the preparation of C-glycosylated serines based on catalytic asymmetric hydrogenation of the corresponding enamide esters with the DuPHOS-Rh+ catalysts. Here we report further development of the methodology in the preparation of the C-glycosyl serine analogue of the p(k) trisaccharide (alpha-Gal(1->4)beta-Gal(1->4)beta-Glc-CH2-serine); we require these ligands for our continuing investigations of the binding subunit of the shiga-like toxin. Catalytic asymmetric hydrogenation was used to prepare both alpha- and beta-C-glycosides in the R and S serine series. We report here on the tolerance of the DuPHOS catalysts toward acetate, benzoate, and benzyl hydroxyl protecting groups. Additionally, we have developed an amino acid protecting group strategy compatible with both asymmetric hydrogenation and solid-phase peptide synthesis. In the course of our studies, we have also developed a new methodology for regioselective reductive cleavage of benzylidene protecting groups.

  DOI：

  10.1021/jo991096m
• 作为产物：
  描述：

  乙酸酐 、 1-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(β-D-galactopyranosyl)-(1->4)-α-D-glucopyranosyl)-2-propene 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 15.0h， 以93%的产率得到1-((2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl)-2-propene
  参考文献：
  名称：

  Synthesis of α- and β-Carbon-Linked Serine Analogues of the P^k Trisaccharide

  摘要：

  The synthesis of glycopeptide ligands for a range of biomedically relevant carbohydrate -binding proteins is a topic of great importance to the glycobiology community. This task is impeded by the inherent instability of glycosyl linkages to serine/threonine, the normal sites of O-glycosylation in proteins. We have previously developed methodology for the preparation of C-glycosylated serines based on catalytic asymmetric hydrogenation of the corresponding enamide esters with the DuPHOS-Rh+ catalysts. Here we report further development of the methodology in the preparation of the C-glycosyl serine analogue of the p(k) trisaccharide (alpha-Gal(1->4)beta-Gal(1->4)beta-Glc-CH2-serine); we require these ligands for our continuing investigations of the binding subunit of the shiga-like toxin. Catalytic asymmetric hydrogenation was used to prepare both alpha- and beta-C-glycosides in the R and S serine series. We report here on the tolerance of the DuPHOS catalysts toward acetate, benzoate, and benzyl hydroxyl protecting groups. Additionally, we have developed an amino acid protecting group strategy compatible with both asymmetric hydrogenation and solid-phase peptide synthesis. In the course of our studies, we have also developed a new methodology for regioselective reductive cleavage of benzylidene protecting groups.

  DOI：

  10.1021/jo991096m