2-(trimethylsilyl)ethyl 2-azido-6-O-benzoyl-2-deoxy-β-D-galactopyranoside | 151651-23-9

• 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-azido-6-O-benzoyl-2-deoxy-β-D-galactopyranoside
• 英文别名: 2-(trimethylsilyl)ethyl 2-azido-6-O-benzyl-2-deoxy-β-D-galactopyranoside；[(2R,3R,4R,5R,6R)-5-azido-3,4-dihydroxy-6-(2-trimethylsilylethoxy)oxan-2-yl]methyl benzoate
• CAS: 151651-23-9
• 化学式: C₁₈H₂₇N₃O₆Si
• 分子量: 409.514
• InChiKey: PMMZPFPNSQAHLS-XLKGFZLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.32
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  99.6
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  O-ethyl S-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-α-D-glycero-D-galacto-2-nonulopyranosyl)onate] dithiocarbonate 、 2-(trimethylsilyl)ethyl 2-azido-6-O-benzoyl-2-deoxy-β-D-galactopyranoside 在 3 A molecular sieve 、 silver trifluoromethanesulfonate 、 一溴化碘 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 2.0h， 以89%的产率得到(4S,5R,6R)-4-Acetoxy-5-acetylamino-2-[(2R,3R,4R,5R,6R)-3-azido-6-benzoyloxymethyl-5-hydroxy-2-(2-trimethylsilanyl-ethoxy)-tetrahydro-pyran-4-yloxy]-6-((1S,2R)-1,2,3-triacetoxy-propyl)-tetrahydro-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  卤素间/三氟甲磺酸银作为高产唾液酸化促进剂体系的研究。

  摘要：

  我们研究了卤素/银三氟甲磺酸盐（IX / AgOTf）促进的糖基化，发现形成的氧碳鎓离子（例如来自具有或不具有参与基团的化合物）对卤代亲核试剂的敏感性差异。这些差异可以使用HSAB理论来解释。通过将该理论应用于唾液酸化反应，我们将模型反应的产率从使用ICl的高度不可预测的35-46％提高到了使用IBr的74％。我们还表明，银离子最主要的作用是降低卤化物亲核试剂的浓度，而不是活化卤素间化合物，并且通过将AgOTf的量从1当量提高到1.5当量（相对于IBr），可以提高模型反应从74％提高到89％。对两个不同的异头离去基团的比较表明，使用硫代苯基供体而不是黄药可以最小化糖基的形成。通过结合这些观察，我们能够将模型反应的产率提高到97％。

  DOI：

  10.1021/jo0262412
• 作为产物：
  描述：

  Benzoic acid (3aR,4R,6R,7R,7aR)-7-azido-2,2-dimethyl-6-(2-trimethylsilanyl-ethoxy)-tetrahydro-[1,3]dioxolo[4,5-c]pyran-4-ylmethyl ester 在 溶剂黄146 作用下， 反应 1.67h， 生成 2-(trimethylsilyl)ethyl 2-azido-6-O-benzoyl-2-deoxy-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of Ganglioside Lactams Corresponding to GM1-, GM2-, GM3-, and GM4-Ganglioside Lactones

  摘要：

  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.

  DOI：

  10.1021/ja00122a002

文献信息

• 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.
• Highly Stereoselective .alpha.-Sialylation. Synthesis of GM3-Saccharide and a Bis-Sialic Acid Unit
  作者：Teddy Ercegovic、Goeran Magnusson

  DOI：10.1021/jo00116a022

  日期：1995.6

  The novel sialyl donor methyl [ethyl 5-acetamido-4,7,8,9-tetra-O-acetyl-2-thio-3-(phenylthic)-2,3,5- trideoxy-D-erythro -alpha-L-gluco-2-nonulopyranosid]onate (6) was synthesized in six steps from N-acetylneuraminic acid in an overall yield of 47%. Donor 6 was shown to be superior to conventional sialyl donors in that the sialylation yields were higher, even with sterically hindered and unreactive sialyl accepters, and the alpha/beta-selectivity was virtually complete.
• Study of Interhalogens/Silver Trifluoromethanesulfonate as Promoter Systems for High-Yielding Sialylations
  作者：Andréas Meijer、Ulf Ellervik

  DOI：10.1021/jo0262412

  日期：2002.10.1

  halide nucleophile rather than activating the interhalogen compound and, by increasing the amount of AgOTf from 1 to 1.5 equiv (with respect to IBr), the yield in the model reaction improved from 74% to 89%. A comparison of two different anomeric leaving groups showed that glycal formation can be minimized using a thiophenyl donor instead of xanthate. By combining these observations, we were able to increase

  我们研究了卤素/银三氟甲磺酸盐（IX / AgOTf）促进的糖基化，发现形成的氧碳鎓离子（例如来自具有或不具有参与基团的化合物）对卤代亲核试剂的敏感性差异。这些差异可以使用HSAB理论来解释。通过将该理论应用于唾液酸化反应，我们将模型反应的产率从使用ICl的高度不可预测的35-46％提高到了使用IBr的74％。我们还表明，银离子最主要的作用是降低卤化物亲核试剂的浓度，而不是活化卤素间化合物，并且通过将AgOTf的量从1当量提高到1.5当量（相对于IBr），可以提高模型反应从74％提高到89％。对两个不同的异头离去基团的比较表明，使用硫代苯基供体而不是黄药可以最小化糖基的形成。通过结合这些观察，我们能够将模型反应的产率提高到97％。
• 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.