Methyl <2-(trimethylsilyl)ethyl 5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-(p-methoxybenzyl)-D-glycero-α-D-galacto-2-nonulopyranosid>onate | 164030-10-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl <2-(trimethylsilyl)ethyl 5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-(p-methoxybenzyl)-D-glycero-α-D-galacto-2-nonulopyranosid>onate
• 英文别名: 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-p-methoxybenzyl-D-glycero-α-D-galacto-non-2-ulopyranosid)onate；methyl (2R,4S,5R,6R)-5-acetamido-4-benzoyloxy-6-[(1R,2R)-1,2-dihydroxy-3-[(4-methoxyphenyl)methoxy]propyl]-2-(2-trimethylsilylethoxy)oxane-2-carboxylate
• CAS: 164030-10-8
• 化学式: C₃₂H₄₅NO₁₁Si
• 分子量: 647.795
• InChiKey: GDZGFVRFXGEZCM-DLJNZENESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  45
• 可旋转键数：
  17
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  159
• 氢给体数：
  3
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  Methyl <2-(trimethylsilyl)ethyl 5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-(p-methoxybenzyl)-D-glycero-α-D-galacto-2-nonulopyranosid>onate 、 methyl onate 在 甲磺酰溴 、 MS (3 Angstroem) 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 4.5h， 以44%的产率得到methyl [2-(trimethylsilyl)ethyl (methyl 4,7,8,9-tetra-O-acetyl-5-N,N-diacetylamino-3,5-dideoxy-3-phenylthio-D-erythro-β-L-gluco-non-2-ulopyranosylonate)-(2->8)-5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-p-methoxybenzyl-D-glycero-α-D-galacto-non-...]
  参考文献：
  名称：

  一种新型的立体选择性α-唾液酸化供体；α（2-8）连接的双唾液酸单元的高效合成

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(99)00175-6
• 作为产物：
  描述：

  (2R,4S,5R,6R)-5-Acetylamino-4-benzoyloxy-6-[(4R,5R)-5-hydroxy-2-(4-methoxy-phenyl)-[1,3]dioxan-4-yl]-2-(2-trimethylsilanyl-ethoxy)-tetrahydro-pyran-2-carboxylic acid methyl ester 在 三氯化铝 、 硼烷-三甲胺络合物 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 Methyl <2-(trimethylsilyl)ethyl 5-acetamido-4-O-benzoyl-3,5-dideoxy-9-O-(p-methoxybenzyl)-D-glycero-α-D-galacto-2-nonulopyranosid>onate
  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

• 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.