Methyl onate | 156726-99-7

• 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: Methyl onate
• 英文别名: methyl onate；methyl (ethyl 4,7,8,9-tetra-O-acetyl-5-acetamido-3,5-dideoxy-3-phenylthio-2-thio-D-erythro-β-L-gluco-non-2-ulopyranosid)onate；5-(Acetylamino)-5-deoxy-3-S-phenyl-2-S-ethyl-2,3-dithio-D-erythro-alpha-L-gluco-2-nonulopyranosonic Acid Methyl Ester 2,4,7,8,9-Pentaacetate；methyl (2R,3S,4R,5S,6R)-5-acetamido-4-acetyloxy-2-ethylsulfanyl-3-phenylsulfanyl-6-[(1S,2R)-1,2,3-triacetyloxypropyl]oxane-2-carboxylate
• CAS: 156726-99-7
• 化学式: C₂₈H₃₇NO₁₂S₂
• 分子量: 643.733
• InChiKey: CBZNDOIJCAZHDR-ZPOMJJLZSA-N

物化性质

• 沸点：
  720.5±60.0 °C(predicted)
• 密度：
  1.32±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  43
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  220
• 氢给体数：
  1
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  Methyl onate 在 吡啶 、 甲磺酰溴 、 MS (3 Angstroem) 、 silver trifluoromethanesulfonate 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 34.5h， 生成
  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：

  在 吡啶 、 4-二甲氨基吡啶 、 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 反应 19.0h， 生成 Methyl onate
  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

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.
• Synthesis of Lactam and Acetamido Analogues of Sialyl Lewis x Tetrasaccharide and Lewis x Trisaccharide
  作者：Ulf Ellervik、Hans Grundberg、Göran Magnusson

  DOI：10.1021/jo981204p

  日期：1998.12.1

  Virtually complete regioselective galactosylation of the diol acceptor p-methoxyphenyl 6-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (15) with the donors ethyl 3,4-di-O-acetyl-6-O-benzyl-2-deoxy-2-[[(2,2,2-trichloroethoxy)carbonyl]amino]-1-beta-D-galactopyranoside (14), 4-methylphenyl 2,3-di-O-acetyl-4-azido-6-O-benzyl-4-deoxy-1-thio-beta-D-galactopyranoside (30), and 4-methylphenyl 2-O-acetyl-4-azido-6-O-benzyl-4-deoxy-3-O-(methoxyethanoyl)-1-thio-beta-D-galactopyranoside (44) gave the lactose-diamine derivatives 16, 33, and 45, respectively. Fucosylation of the NHAc derivatives of 16 and 33 (17 and 34) with the donor 18 gave, after deprotection and N-acetylation, the 2-NHAc-Le(x) and 4-NKAc-Le(x) trisaccharides 3 and 5, respectively. Removal of the Troc group from the tetrasaccharide intermediate 23, followed by N-acetylation (-->24), gave the NHAc-SLe(x) tetrasaccharide 2. Regioselective sialylation of the partially protected trisaccharide diols 21 and 37 with the sialyl donors 22 and 38 gave, after deprotection and lactamization, the SLe(x)-1'''-->2-lactam 1 and the SLe(x)-1'''-->4'-lactam 4, respectively. The stannylidene acetal of the trisaccharide diol 21 was regioselectively 3-O-alkylated with tert-butyl bromoacetate; reductive removal of the Tree protecting group and addition of methanolic MeONa caused formation of a lactam ring. Compound 40 was thus obtained over four steps in an overall yield of 52%. Deprotection of 40 furnished the Le(x)-3,2-lactam 6 in 74% yield. Fucosylation of the lactose-diamine derivative 46 with donor 18 gave the N-3-Le(x) trisaccharide derivative 47. The azido function of 47 was reduced with H2S, which caused spontaneous closure of a lactam ring. Removal of the protecting groups then gave the Le(x)-3,4-lactam 7. The total yields of 1, 2, 3, 4, 5, and 7 from the monosaccharide starting materials 14, 15, 18, 22, 30, 38, and 44 were 10%, 10%, 22%, 14%, 62%, and 28%, respectively.
• 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.
• Synthesis of a Bis(sialic acid) 8,9-Lactam
  作者：Teddy Ercégovic、Göran Magnusson

  DOI：10.1021/jo950994p

  日期：1996.1.1

  Methyl [2-(trimethylsilyl)ethyl 5-acetamido-9-azido-4-O-benzoyl-3,5,9-trideoxy-D-glycero-alpha-D-galacto- 2-nonulopyranosid]onate was sialylated with methyl (ethyl 5-acetamido-4,7,8,9-tetra-O-acetyl-2-thio-3-(phenylthio)- 2,3,5-trideoxy-D-erythro-alpha-L-gluco-2-nonulopyranosid)onate to give the corresponding bis(sialic acid) derivative in 23% yield. Removal of protecting groups, reduction of the azido group to an amino group, and removal of the auxiliary thiophenyl group gave the desired bis(sialic acid) 8,9-lactam. Comparison of the H-1 NMR spectra and energy-minimized (MM3) structures of the bis(sialic acid) lactam with those of the corresponding bis(sialic acid) lactone showed the conformations of the two compounds to be very similar (RMS = 0.027 Angstrom).