N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-2-ethylsulfanyl-5-hydroxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide | 174004-01-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-2-ethylsulfanyl-5-hydroxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide
• CAS: 174004-01-4
• 化学式: C₄₅H₈₃NO₁₂S₂Si₃
• 分子量: 978.542
• InChiKey: DCXNDIKJUZMQJV-HGJLHEJPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.96
• 重原子数：
  63
• 可旋转键数：
  22
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  191
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-2-ethylsulfanyl-5-hydroxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide 、 (2R,3R,4S,5R,6R)-2-[(2R,3S,4S,5R,6S)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]oxan-3-yl]oxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-ol 在 4 A molecular sieve 、 三氟甲烷磺酸甲酯 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 7.0h， 以61%的产率得到N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-2-[(2R,3R,4S,5S,6R)-2-[(2R,3S,4S,5R,6S)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-[[(2R,3S,4R)-4-phenylmethoxy-2-(phenylmethoxymethyl)-3,4-dihydro-2H-pyran-3-yl]oxy]oxan-3-yl]oxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-yl]oxy-5-hydroxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide
  参考文献：
  名称：

  A total synthesis of a stage specific pentasaccharide embryogenesis marker

  摘要：

  A thioglycoside coupling mediated by methyl triflate was used to generate Stage Specific Embryonic Antigen-3.

  DOI：

  10.1016/0040-4039(95)01962-h
• 作为产物：
  描述：

  2,6-脱水-5-脱氧-3,4-O-(氧代亚甲基)-1-O-(三异丙基硅烷基)-D-阿拉伯糖-己-5-烯糖 在 咪唑 、 iodonium(di-γ-collidine) perchlorate 、 二甲基二环氧乙烷 、 zinc(II) chloride 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 15.17h， 生成 N-[(2S,3R,4R,5R,6R)-4-[[(3aS,4R,6R,7R,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-2-oxo-4-[tri(propan-2-yl)silyloxymethyl]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-6-yl]oxy]-2-ethylsulfanyl-5-hydroxy-6-[tri(propan-2-yl)silyloxymethyl]oxan-3-yl]benzenesulfonamide
  参考文献：
  名称：

  Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation

  摘要：

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.

  DOI：

  10.1021/ja9724957

文献信息

• A Total Synthesis of the Methyl Glycoside of Ganglioside GM₁
  作者：Samit K. Bhattacharya、Samuel J. Danishefsky

  DOI：10.1021/jo9912496

  日期：2000.1.1

  The total synthesis of the methyl glycoside of GM(1) (1b) has been accomplished. The key step in the synthesis involves the sulfonamidoglycosidation reaction, which is used to create a beta-linkage leading to a GalNAc residue joined to the C4 hydroxyl group of a galactose unit of a C3 sialylated lactosyl moiety. The "proximal hydroxyl" directing effect, which has been postulated before, manifests in

  GM（1）（1b）甲基糖苷的总合成已完成。合成中的关键步骤涉及磺酰胺基糖苷化反应，该反应用于产生β键，导致连接到C3唾液酸化乳糖基部分的半乳糖单元的C4羟基的GalNAc残基。在这种情况下，还出现了以前假定的“近端羟基”导向作用，并导致β-糖苷的大量形成。连同积雪草GM（1）和其他子结构，GM（1）甲基糖苷已被提交用于生物学检测，作为细菌和病毒感染部位的潜在配体。
• Synthesis of Asialo GM₁. New Insights in the Application of Sulfonamidoglycosylation in Oligosaccharide Assembly:  Subtle Proximity Effects in the Stereochemical Governance of Glycosidation
  作者：Ohyun Kwon、Samuel J. Danishefsky

  DOI：10.1021/ja9724957

  日期：1998.2.1

  The total synthesis of asialo GM(1) (1a) has been accomplished, Using related chemistry, the methyl glycoside of the asialo compound (1b) has also been synthesized. These kinds of compounds have been identified as potential ligands for bacterial and viral infection sites, A simpler structure, which hits also been identified for its infection attracting structure in the context of glycopeptides and glycolipids (methyl glycoside 2), has also been synthesized. The key common phase in the syntheses involves the sulfonamidoglycosidation reaction which is used to create a beta-linkage leading to a galNAc residue joined to the C-4 hydroxyl group of a galactose unit either as a monosaccharide (see compound 2) or as C-4' in the contest of a lactosyl moiety, During the course of these studies there was encountered an unusual "proximal hydroxyl" directing effect. Thus, when C-4 on the galactose ring of an azaglycosylating donor bears a free hydroxyl (see, for instance, compound 13), beta-glycoside formation predominates. When this hydroxyl group is blocked, the process tends in the direction of alpha-glycoside formation (see compound 32), These findings were explained as arising from a critical intramolecular hydrogen bond between the C-4 axial hydroxyl of the galactose donor and its proximal pyranosidal ring oxygen. This interaction stabilizes conformations from which beta-glycosidation predominates.
• A total synthesis of a stage specific pentasaccharide embryogenesis marker
  作者：Tae Kyo Park、In Jong Kim、Samuel J. Danishefsky

  DOI：10.1016/0040-4039(95)01962-h

  日期：1995.12

  A thioglycoside coupling mediated by methyl triflate was used to generate Stage Specific Embryonic Antigen-3.