2-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-<2,4,6-tri-O-benzyl-3-O-onate>-β-D-galactopyranosyl>-β-D-glucopyranoside | 156727-00-3

• 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-<2,4,6-tri-O-benzyl-3-O-onate>-β-D-galactopyranosyl>-β-D-glucopyranoside
• 英文别名: 2-(trimethylsilyl)ethyl (methyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-3-phenylthio-D-erythro-β-L-gluco-non-2-ulopyranosylonate)-(2->3)-(2,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside；2-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-(2,4,6-tri-O-benzyl-3-O-{methyl [5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-3-(phenylthio)-D-erythro-α-L-gluco-2-nonulopyranosyl]onate}-β-D-galactopyranosyl)-β-D-glucopyranoside；methyl (2R,3S,4R,5S,6R)-5-acetamido-4-acetyloxy-2-[(2S,3R,4S,5S,6R)-2-[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-6-(2-trimethylsilylethoxy)oxan-3-yl]oxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-yl]oxy-3-phenylsulfanyl-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 156727-00-3
• 化学式: C₈₅H₁₀₁NO₂₃SSi
• 分子量: 1564.88
• InChiKey: DRVMUNZXBVFQAO-IFHYWNEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.63
• 重原子数：
  111
• 可旋转键数：
  44
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  297
• 氢给体数：
  1
• 氢受体数：
  24

反应信息

• 作为反应物：
  描述：

  2-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-<2,4,6-tri-O-benzyl-3-O-onate>-β-D-galactopyranosyl>-β-D-glucopyranoside 在 偶氮二异丁腈 、 三苯基氢化锡 作用下， 以 甲苯 为溶剂， 反应 14.0h， 以83%的产率得到2-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-<2,4,6-tri-O-benzyl-3-O-onate>-β-D-galactopyranosyl>-β-D-glucopyranoside
  参考文献：
  名称：

  A new N-acetylneuraminic acid donor for highly stereoselective α-sialylation

  摘要：

  新型唾液酸供体6（由N-乙酰神经氨酸经过六个步骤以44%的产率制备）能够以67%的产率对2-(三甲基硅基)乙基2,3,6,2'、4'、6'-六苄基-β-D-乳糖苷进行干净的α-唾液酸化反应。

  DOI：

  10.1039/c39940000831
• 作为产物：
  描述：

  Methyl onate 、 在 甲基硫基溴化物 、 3 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 1,2-二氯乙烷 、 乙腈 为溶剂， 以67%的产率得到2-(Trimethylsilyl)ethyl 2,3,6-tri-O-benzyl-4-O-<2,4,6-tri-O-benzyl-3-O-onate>-β-D-galactopyranosyl>-β-D-glucopyranoside
  参考文献：
  名称：

  Highly Stereoselective .alpha.-Sialylation. Synthesis of GM3-Saccharide and a Bis-Sialic Acid Unit

  摘要：

  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.

  DOI：

  10.1021/jo00116a022

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.