2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-β-D-glucopyranoside | 139244-25-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-β-D-glucopyranoside
• 英文别名: 2-(trimethylsilyl)ethyl (2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside；(2R,3R,4R,5R,6S)-5-azido-6-[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-(2-trimethylsilylethoxy)oxan-3-yl]oxy-2-(phenylmethoxymethyl)oxane-3,4-diol
• CAS: 139244-25-0
• 化学式: C₄₅H₅₇N₃O₁₀Si
• 分子量: 828.047
• InChiKey: PQZGNOWIYLQXMZ-PPTXHGBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.18
• 重原子数：
  59
• 可旋转键数：
  21
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  129
• 氢给体数：
  2
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-β-D-glucopyranoside 在 palladium on activated charcoal 吡啶 、 sodium tetrahydroborate 、 甲磺酰溴 、 3 A molecular sieve 、 氢气 、 sodium methylate 、 silver trifluoromethanesulfonate 、 硼酸 、 二异丙胺 、 nickel dichloride 作用下， 以 甲醇 、 乙醇 为溶剂， -78.0~22.0 ℃ 、101.33 kPa 条件下， 反应 27.33h， 生成 2-(trimethylsilyl)ethyl 4-O-<2-amino-2-deoxy-3-O-(5-acetamido-3,5-dideoxy-D-glycero-α-D-galacto-2-nonulopyranosyloyl-1''<*>2'-lactam)-β-D-galactopyranosyl>-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis and conformational analysis of GM3 lactam; a hydrolytically stable analog of GM3 ganglioside lactone

  摘要：

  DOI：

  10.1021/ja00032a049
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-galactopyranosyl bromide 生成 2-(trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis and conformational analysis of GM3 lactam; a hydrolytically stable analog of GM3 ganglioside lactone

  摘要：

  DOI：

  10.1021/ja00032a049

文献信息

• Arynes in the Monoarylation of Unprotected Carbohydrate Amines
  作者：Kumar Bhaskar Pal、Mukul Mahanti、Ulf J. Nilsson

  DOI：10.1021/acs.orglett.7b03741

  日期：2018.2.2

  A CsF-mediated method has been developed for the N-arylation of amino sugars that affords good to excellent yields of arylated products under mild conditions involving the in situ generation of arynes. The reaction conditions tolerate a variety of common carbohydrate protecting groups and also performs exceptionally well on unprotected amino sugar derivatives. The reactions are scalable in moderate

  已经开发出用于氨基糖的N-芳基化的CsF介导的方法，其在涉及原位生成芳烃的温和条件下提供良好至优异的芳基化产物收率。反应条件可耐受多种常见的碳水化合物保护基，并且在未保护的氨基糖衍生物上也表现出色。反应范围宽广，可以中等至良好的收率进行扩展。
• Synthesis of GD3-lactam: a potential ligand for the development of an anti-melanoma vaccine
  作者：Nafizal Hossain、Amparo Zapata、Mikael Wilstermann、Ulf J. Nilsson、Göran Magnusson

  DOI：10.1016/s0008-6215(02)00036-8

  日期：2002.4

  The novel sialyl donor methyl (ethyl 4,7,8,9-tetra-O-acetyl-5-N,N-diacetylamino-3,5-dideoxy-2-thio-3-thiophenyl-D-erthro-beta-L-gluco-non-2-ulopyranosid)onate was used for glycosylation of a lactosyl acceptor to give the GM3-trisaccharide derivative in 83% yield. Introduction of an azido group at C-9" of the GM3-trisaccharide derivative, transformation into a glycosyl acceptor, and sialylation with the above mentioned novel sialyl donor gave a GD3-trisaccharide in 50% yield. Reduction of the azido group gave the corresponding amine, which underwent spontaneous lactamization to the GD3-[1'''-9"]-lactam in an overall yield of 86%. Removal of protecting groups of over five steps, followed by per-O-acetylation gave an acetylated GD3-[1'''-9"]-lactam TMSEt glycoside in 27% overall yield. The acetylated GD3-[1'''-9"]-lactam TMSEt glycoside is suitable for glycosylation of linker-arms and the resulting linker-glycosides are planned to be coupled to carrier proteins. thus providing immunogens for trial vaccinations against malignant melanoma. (C) 2002 Elsevier Science Ltd. All rights reserved.
• 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.