2-(trimethylsilyl)ethyl (2,6-di-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3-di-O-acetyl-β-D-xylopyranoside | 197144-01-7

• 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: 2-(trimethylsilyl)ethyl (2,6-di-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3-di-O-acetyl-β-D-xylopyranoside
• 英文别名: Gal2Ac6Ac(b1-4)Xyl2Ac3Ac(b)-O-EtTMS；[(2R,3R,4S,5R,6S)-5-acetyloxy-6-[(3R,4S,5R,6S)-4,5-diacetyloxy-6-(2-trimethylsilylethoxy)oxan-3-yl]oxy-3,4-dihydroxyoxan-2-yl]methyl acetate
• CAS: 197144-01-7
• 化学式: C₂₄H₄₀O₁₄Si
• 分子量: 580.659
• InChiKey: RRIYKTFEHDWCEQ-VENQHLRYSA-N

物化性质

• 沸点：
  620.6±55.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.11
• 重原子数：
  39
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  183
• 氢给体数：
  2
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl (2,6-di-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3-di-O-acetyl-β-D-xylopyranoside 在 甲磺酰溴 、 silver trifluoromethanesulfonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 二异丙胺 、 三氟乙酸 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 9.75h， 生成 methyl (2S,4S,5R,6R)-5-acetamido-4-acetyloxy-2-[(2R,3S,4S,5R,6S)-3,5-diacetyloxy-2-(acetyloxymethyl)-6-[(3R,4S,5R)-4,5-diacetyloxy-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl]oxyoxan-4-yl]oxy-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
  参考文献：
  名称：

  Synthesis of XylβCer, Galβ1−4XylβCer, NeuAcα2−3Galβ1−4XylβCer and the Corresponding Lactone and Lactam Trisaccharides

  摘要：

  2-(Trimethylsilyl)ethyl 2-O-benzoyl- and 2,3-di-O-acetyl-beta-D-xylopyranosides (12 and 14) were synthesized in high yields and subjected to glycosylation with various glycosyl donors. Galactosylation of 12 gave the xylose analogue of TMSEt lactoside (3), which was transformed into the glycosyl acceptor 19. Sialylation then gave the xylose analogue of G(M3) trisaccharide (5). The TMSEt glycosides 10, 25, and 32 were transformed into the corresponding trichloroacetimidates, which were used for glycosylation of an azidosphingosine derivative. The resulting sphingosyl glycosides were transformed into the title ceramides. Treatment of NeuAc alpha 2-3Gal beta 1-4Xyl beta Cer (5) with acetic acid gave the corresponding l''-2'-lactone 7. Glycosylation of 12 or 14 with a G(M4)-lactam donor (40) gave the xylose analogue of G(M3)-lactam (42). There was a 3-fold increase in the formation of GAG chains in the presence of 0.5 mu M Xyl beta Cer (2) in the medium.

  DOI：

  10.1021/jo970298k
• 作为产物：
  描述：

  2,3,4-三-O-乙酰基-α-D-木吡喃糖苷溴 在 4-二甲氨基吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 MS 300AW 、 四丁基氟化铵 、 sodium methylate 、 对甲苯磺酸 、 溶剂黄146 、 三乙胺 、 mercury dibromide 、 mercury(II) oxide 作用下， 以 吡啶 、 甲醇 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 86.25h， 生成 2-(trimethylsilyl)ethyl (2,6-di-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3-di-O-acetyl-β-D-xylopyranoside
  参考文献：
  名称：

  Synthesis of XylβCer, Galβ1−4XylβCer, NeuAcα2−3Galβ1−4XylβCer and the Corresponding Lactone and Lactam Trisaccharides

  摘要：

  2-(Trimethylsilyl)ethyl 2-O-benzoyl- and 2,3-di-O-acetyl-beta-D-xylopyranosides (12 and 14) were synthesized in high yields and subjected to glycosylation with various glycosyl donors. Galactosylation of 12 gave the xylose analogue of TMSEt lactoside (3), which was transformed into the glycosyl acceptor 19. Sialylation then gave the xylose analogue of G(M3) trisaccharide (5). The TMSEt glycosides 10, 25, and 32 were transformed into the corresponding trichloroacetimidates, which were used for glycosylation of an azidosphingosine derivative. The resulting sphingosyl glycosides were transformed into the title ceramides. Treatment of NeuAc alpha 2-3Gal beta 1-4Xyl beta Cer (5) with acetic acid gave the corresponding l''-2'-lactone 7. Glycosylation of 12 or 14 with a G(M4)-lactam donor (40) gave the xylose analogue of G(M3)-lactam (42). There was a 3-fold increase in the formation of GAG chains in the presence of 0.5 mu M Xyl beta Cer (2) in the medium.

  DOI：

  10.1021/jo970298k

文献信息

• A novel donor for stereoselective α-sialylation; efficient synthesis of an α(2–8)-linked bis-sialic acid unit
  作者：Nafizal Hossain、Göran Magnusson

  DOI：10.1016/s0040-4039(99)00175-6

  日期：1999.3

  The novel sialyl donor methyl 5-(N,N-diacetyl)-4,7,8,9-tetra-O-acetyl-2-thio-3-thiophenyl-2,3,5-trideoxy-D-erythro-α-L-gluco-2-nonulopyranosid]onate (2) was synthesized by N-acetylation of the corresponding 5-acetamido compound 1. α-Sialylation of mono- and disaccharide aglycons, having one or two unprotected hydroxyl groups, furnished the corresponding di- and trisaccharides in high yield and with

  新的唾液酸供体甲基5-（N，N-二乙酰基）-4,7,8,9-四-O-乙酰基-2-硫代-3-硫代苯基-2,3,5-三苯氧基-D-赤型通过对相应的5-乙酰氨基化合物1进行N-乙酰化，合成了-L-葡萄糖-2-壬基吡喃糖苷（2）。具有一个或两个未保护的羟基的单糖和二糖苷元的α-唾液酸化以高收率提供了相应的二糖和三糖，并且具有几乎完全的区域选择性和立体选择性。作为一个实例，因此以44％的收率获得了Neu5Acα（2→8）Neu5Ac衍生物。没有观察到相应的β端基异构体。
• 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.