4-(trichloroacetamido)phenyl 2-deoxy-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-galactopyranoside | 500213-06-9

• 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: 4-(trichloroacetamido)phenyl 2-deoxy-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-galactopyranoside
• 英文别名: 4-trichloroacetamidophenyl 4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-galactopyranoside
• CAS: 500213-06-9
• 化学式: C₃₄H₃₈Cl₆N₂O₁₇S
• 分子量: 991.463
• InChiKey: BWTRPBRWPREEJH-GCISUABHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.63
• 重原子数：
  60.0
• 可旋转键数：
  14.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  243.69
• 氢给体数：
  2.0
• 氢受体数：
  18.0

反应信息

• 作为反应物：
  描述：

  4-(trichloroacetamido)phenyl 2-deoxy-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-galactopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.33h， 生成 2,2,2-Trichloro-N-[(2S,3R,4R,5R,6R)-5-hydroxy-6-hydroxymethyl-2-[4-(2,2,2-trichloro-acetylamino)-phenylsulfanyl]-4-((2R,3R,4S,5R,6R)-3,4,5-trihydroxy-6-hydroxymethyl-tetrahydro-pyran-2-yloxy)-tetrahydro-pyran-3-yl]-acetamide
  参考文献：
  名称：

  Synthesis of aminoethyl glycoside of the oligosaccharide chain of ganglioside Fuc-GM1

  摘要：

  通过[3+3]合成方案合成了神经节苷脂 Fuc-GM1 六糖链的 2-氨基乙基糖苷。在合成路线的关键步骤、在合成路线的关键步骤中，将α-(N-乙酰神经氨酸基)-(2→3)-β-D-吡喃半乳糖基-(1→4)-β-D-吡喃葡萄糖苷衍生物中半乳糖残基 C(4)处的唯一羟基与α-L-吡喃葡萄糖基-(1→4)-β-D-吡喃葡萄糖苷的过乙酰化硫代糖苷进行糖基化。L-吡喃葡萄糖基-(1→2)-β-D-吡喃半乳糖基-(1→3)-2-三氯乙酰氨基-2-脱氧-β-D-吡喃半乳糖的过乙酰化硫代糖苷衍生物，高产率地得到了受保护的六糖。随后去除保护基团，就得到了甘神经胶质苷 Fuc-GM1 寡糖链的目标 2-氨基乙基糖苷。

  DOI：

  10.1007/s11172-006-0229-8
• 作为产物：
  描述：

  4-nitrophenyl 2-azido-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-β-D-galactopyranoside 在 溶剂黄146 、 三乙胺 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.33h， 生成 4-(trichloroacetamido)phenyl 2-deoxy-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-1-thio-2-trichloroacetamido-β-D-galactopyranoside
  参考文献：
  名称：

  [与二糖β-D-Gal-（1-> 3）-D-GalNAc主链的α-和β-糖基供体的合成]。

  摘要：

  使用一系列适当保护的苯基2的3-单羟基和3,4-二羟基衍生物系列进行糖基化研究了具有二糖β-D-Gal-（1→3）-D-GalNAc主链的硫糖基供体的合成-半乳糖基溴化物，氟化物和三氯乙酰亚氨酸盐形成-叠氮基-2-脱氧-1-硫基-硫代α-和1-硫基-β-D-吡喃半乳糖苷。在与单羟基化的糖基受体的反应中，硫代苯基从糖基受体的分子间转移到由糖基供体分子形成的阳离子上的过程占主导。在相同条件下将3,4-二醇糖基化时，形成的硫代苯基转移产物占主导地位或形成了不希望的（1→4）而非（1→3）连接的二糖产物。当用4-硝基苯硫基取代半乳糖基受体分子中的苯硫基时，糖苷配基转移被排除在外。这产生了目标二糖，4-硝基苯基2-叠氮基-4,5-O-亚苄基-2-脱氧-3-O-（2,3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基）-1-硫代-β-D-吡喃半乳糖苷，产率为57％。该二糖产物在半乳糖胺的2位带有非参与叠

  DOI：

  10.1023/a:1020428329743

文献信息

• ——
  作者：P. E. Cheshev、E. A. Khatuntseva、A. G. Gerbst、Yu. E. Tsvetkov、A. S. Shashkov、N. E. Nifantiev

  DOI：10.1023/a:1024905419008

  日期：——

  selectively protected derivatives of tetrasaccharide GalNAc(beta 1-->3)Gal(alpha 1-->4)Gal(beta 1-->4)Glc beta-OCH2CH2N3 and pentasaccharide Gal(beta 1-->3)GalNAc(beta 1-->3)Gal(alpha 1-->4)Gal(beta 1-->4)Glc beta-OCH2CH2N3 in 88 and 73% yields, respectively. Removal of O-protecting groups, substitution of acetyl group for N-trichloroacetyl group, and reduction of the aglycone azide group resulted in the

  6-三-O-乙酰基-2-脱氧-1-硫代-2-三氯乙酰氨基-β-D-吡喃半乳糖苷和4-三氯乙酰胺基苯基4,6-二-O-乙酰基-2-脱氧-3-O-（2，在N-碘代琥珀酰亚胺和三氟甲磺酸存在下，二氯甲烷中的3,4,6-四-O-乙酰基-β-D-吡喃半乳糖基）-1-硫-2-三氯乙酰胺基-β-D-吡喃半乳糖苷导致相应的选择性保护四糖GalNAc（β1-> 3）Gal（α1-> 4）Gal（β1-> 4）Glcβ-OCH2CH2N3的衍生物和五糖Gal（β1-> 3）GalNAc（β1- -> 3）Gal（alpha 1-> 4）Gal（beta 1-> 4）Glc beta-OCH2CH2N3，产率分别为88％和73％。除去O-保护基，将乙酰基替换为N-三氯乙酰基，以及将糖苷配基叠氮基还原，得到目标2-氨基乙基球蛋白三-，-四-和-五糖，
• Synthesis of Aminoethyl Glycosides of the Ganglioside GM₁and Asialo-GM₁Oligosaccharide Chains
  作者：P. E. Cheshev、E. A. Khatuntseva、Yu. E. Tsvetkov、A. S. Shashkov、N. E. Nifantiev

  DOI：10.1023/b:rubi.0000015775.24385.a0

  日期：2004.1

  4'-O-Glycosylation of 2-azidoethyl 2,3,6-tri-O-benzyl-4-O-(2,3-di-O-benzyl-6-O-benzoyl-beta-D-galactopyranosyl)-beta-D-glucopyranoside with a disaccharide donor, 4-trichloroacetamidophenyl 4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-1-thio-2-trichloroacetamido-beta-D-galactopyranoside, in dichloromethane in the presence of N-iodosuccinimide and trifluoromethanesulfonic acid resulted in a tetrasaccharide, 2-azidoethyl (2,3,4,6-tetra-O-acetyl-beta-D-(galactopyranosyl)-(1 --> 3)-(4,6-di-O-acetyl-2-deoxy-2-trichloroacetamido-beta-D-galactopyranosyl)-(1 --> 4)-(2,3-di-O-benzyl-6-O-benzoyl-beta-D-galactopyranosyl)-(1 --> 4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside, in 69% yield. The complete removal of O-protecting groups in the tetrasaccharide, the replacement of N-trichloroacetyl by N-acetyl group, and the reduction of the aglycone azide group to amine led to the target aminoethyl glycoside of beta-D-Gal-(1 --> 3)-beta-D-Gal-NAc-(1 --> 4)-beta-D-Gal-(1 --> 4)-beta-D-Glc-OCH2CH2NH2 containing the oligosaccharide chain of asialo-GM(1) ganglioside in 72% overall yield. Selective 3'-O-glycosylation of 2-azidoethyl 2,3,6-tri-O-benzyl-4-O-(2,6-di-O-benzyl-beta-D-galactopyranosyl)-beta-D-glucopyranoside with thioglycoside methyl (ethyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-2-thio-D-glycero-alpha-D-galacto-2-nonulopyranosyl)oate in acetonitrile in the presence of N-iodosuccinimide and trifluoromethanesulfonic acid afforded 2-azidoethyl [methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosyl)oate]-(2 --> 3)-2,6-di-O-benzyl-beta-D-galactopyranosyl)-(1 --> 4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside, the selectively protected derivative of the oligosaccharide chain of GM(3) ganglioside, in 79% yield. Its 4'-O-glycosylation with a disaccharide glycosyl donor, (4-trichloroacetophenyl-4,6-di-O-acetyl-2-deoxy-3-O-(2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl) 1-thio-2-trichloroacetamido-beta-D-galactopyranoside in dichloromethane in the presence of N-iodosuccinimide and trifluoromethanesulfonic acid gave 2-azidoethyl (2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)-(1 --> 3)-4,6-di-O-acetyl-2-deoxy-2-trichloroacetamido-beta-D-galactopyranosyl)-(1 --> 4)-[methyl (5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha-D-galacto-2-nonulopyranosyl)onate]-(2 --> 3)}-(2,6-di-O-benzyl-beta-D-galactopyranosyl)-(1 --> 4)-2,3,6-tri-O-benzyl-beta-D-glucopyranoside in 85% yield. The resulting pentasaccharide was O-deprotected, its N-trichloroacetyl group was replaced by N-acetyl group, and the aglycone azide group was reduced to afford in 85% overall yield aminoethyl glycoside of beta-D-Gal-(1 --> 3)-beta-D-GalNAc-(1 --> 4)-[alpha-D-Neu5Ac-(2 --> 3)]-beta-D-Gal-(1 --> 4)-beta-D-Glc-OCH2CH2NH2 containing the oligosaccharide chain of GM(1) ganglioside.