2-azidoethyl (2,6-di-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside | 316820-50-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-azidoethyl (2,6-di-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: 2-azidoethyl 2,6-di-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside；2-azidoethyl 2,3,6-tri-O-benzyl-4-O-(2,6-di-O-benzyl-β-D-galactopyranosyl)-β-D-glucopyranoside；2-azidoethyl 2,3,6-tri-O-benzyl-4-O-(2,6-di-O-benzyl-beta-d-galactopyranosyl)-beta-d-glucopyranoside；(2R,3R,4S,5R,6S)-6-[(2R,3R,4S,5R,6R)-6-(2-azidoethoxy)-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-5-phenylmethoxy-2-(phenylmethoxymethyl)oxane-3,4-diol
• CAS: 316820-50-5
• 化学式: C₄₉H₅₅N₃O₁₁
• 分子量: 861.989
• InChiKey: PSJRNCDESJSNFH-GCIZIPIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  63
• 可旋转键数：
  23
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  138
• 氢给体数：
  2
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  2-azidoethyl (2,6-di-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside 、 ethyl (2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-(1->2)-(3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-(1->3)-[(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-(1->4)]-6-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside 在 DMTST 作用下， 以 二氯甲烷 为溶剂， 以72%的产率得到2-azidoethyl (2,3,4-tri-O-benzyl-α-L-Fucp)-(1->2)-(3,4,6-tri-O-benzyl-β-D-Galp)-(1->3)-[2,3,4-tri-O-benzyl-α-L-Fucp-(1->4)]-(6-O-benzyl-2-deoxy-2-phthalimido-β-D-Glcp)-(1->3)-(2,6-di-O-benzyl-β-D-Galp)-(1->4)-2,3,6-tri-O-benzyl-β-D-Glcp
  参考文献：
  名称：

  具有各种糖负载量的路易斯b六糖及其方酸-HSA共轭物的合成。

  摘要：

  Lewis b六糖，α-L-Fucp-（1-> 2）-β-D-Galp-（1-> 3）-[α-L-Fucp-（1-> 4）]-β -D-GlcpNAc-（1→3）-β-D-Galp-（1→4）-β-D-Glcp已经使用收敛合成法合成。从乙基4,6-O-亚苄基-2-脱氧-2-邻苯二甲酰亚胺-1-硫代-β-D-吡喃葡萄糖苷开始，通过与糖基溴化物供体的两次正交糖基化，构建了硫代糖苷四糖供体嵌段。首先，使用三氟甲磺酸银作为促进剂引入半乳糖部分，然后在卤化物辅助条件下引入两个岩藻糖残基。最后，将该四糖以DMTST促进的偶联方式连接到带有间隔基的3I，4I-二醇乳糖受体上，以在脱保护后得到带有2-氨基乙基间隔基的衍生物Lewis b六糖。这与人类血清白蛋白（HSA）偶联，

  DOI：

  10.1016/s0008-6215(00)00189-0
• 作为产物：
  描述：

  1',2',3',6',2,3,4,6-octa-O-acetyl-β-D-lactose 在 氢溴酸 、 sodium methylate 、 氰化汞 、 sodium hydride 、 对甲苯磺酸 、 溶剂黄146 、 三氟乙酸 、 mercury dibromide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 123.0h， 生成 2-azidoethyl (2,6-di-O-benzyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  具有各种糖负载量的路易斯b六糖及其方酸-HSA共轭物的合成。

  摘要：

  Lewis b六糖，α-L-Fucp-（1-> 2）-β-D-Galp-（1-> 3）-[α-L-Fucp-（1-> 4）]-β -D-GlcpNAc-（1→3）-β-D-Galp-（1→4）-β-D-Glcp已经使用收敛合成法合成。从乙基4,6-O-亚苄基-2-脱氧-2-邻苯二甲酰亚胺-1-硫代-β-D-吡喃葡萄糖苷开始，通过与糖基溴化物供体的两次正交糖基化，构建了硫代糖苷四糖供体嵌段。首先，使用三氟甲磺酸银作为促进剂引入半乳糖部分，然后在卤化物辅助条件下引入两个岩藻糖残基。最后，将该四糖以DMTST促进的偶联方式连接到带有间隔基的3I，4I-二醇乳糖受体上，以在脱保护后得到带有2-氨基乙基间隔基的衍生物Lewis b六糖。这与人类血清白蛋白（HSA）偶联，

  DOI：

  10.1016/s0008-6215(00)00189-0

文献信息

• Enhanced Sialylating Activity of O-Chloroacetylated 2-Thioethyl Sialosides
  作者：Yury E. Tsvetkov、Nikolay E. Nifantiev

  DOI：10.1055/s-2005-868514

  日期：——

  It has been shown that O-chloroacetyl protecting groups enhance significantly sialylating activity of 2-thioethyl sialosides in model reactions of α(2-8)-sialylation. Ethyl 4,7,8,9-tetra-O-chloroacetyl-3,5-dideoxy-2-thio-5-trifluoroacetamido-d-glycero-α-d-galacto-non-2-ulopyranoside that combines electron-withdrawing O-chloroacetyl and N-trifluoroacetyl protecting groups displayed the best reactivity and enabled the most efficient synthesis of the Neu5Acα(2-8)Neu5Ac dimer. The GD3 tetrasaccharide was synthesized in stepwise manner using this sialyl donor in the key (2-8)-coupling, albeit the yield was noticeably lower than in the model sialylation of monosaccharide acceptors.

  研究表明，O-氯乙酰保护基团显著提高了2-巯乙基唾液酸苷在α(2-8)-唾液酸化模型反应中的活性。乙基4,7,8,9-四-O-氯乙酰-3,5-二脱氧-2-硫-5-三氟乙酰胺基-d-甘油-α-d-半乳糖-壬-2-烯呋喃糖苷结合了吸电子的O-氯乙酰和N-三氟乙酰保护基团，展现出最佳的反应活性，并实现了Neu5Acα(2-8)Neu5Ac二聚体的最高效合成。通过使用这种唾液酸供体，以分步方式合成了GD3四糖，尽管其产率明显低于单糖受体的模型唾液酸化反应。
• 10.1039/d4md00387j
  作者：Romanò, Cecilia、Jiang, Hao、Tahvili, Sahar、Wei, Peng、Keiding, Ulrik B.、Clergeaud, Gael、Skovbakke, Sarah Line、Blomberg, Anne Louise、Hafkenscheid, Lise、Henriksen, Jonas R.、Andresen, Thomas L.、Goletz, Steffen、Hansen, Anders E.、Christensen, Dennis、Clausen, Mads H.

  DOI：10.1039/d4md00387j

  日期：——

  system – have emerged as central players in cancer vaccine therapies. Glycolipids activating iNKT cells, such as α-galactosylceramide (αGalCer), can enhance the immune response against co-delivered cancer antigens and have been applied in the design of self-adjuvanting anti-tumor vaccines. In this context, this work focuses on the chemical synthesis of ganglioside tumor-associated carbohydrate antigens

  iNKT 细胞通常被称为免疫系统的“瑞士军刀”，已成为癌症疫苗治疗的核心角色。激活iNKT细胞的糖脂，例如α-半乳糖神经酰胺（αGalCer），可以增强针对共同传递的癌症抗原的免疫反应，并已应用于自我辅助抗肿瘤疫苗的设计。在此背景下，这项工作重点是神经节苷脂肿瘤相关碳水化合物抗原（TACA）的化学合成，即 GM3 和 (Neu5Gc)GM3 抗原，它们与 αGalCer 的缀合，以及它们配制到脂质体中作为其体内递送的有效平台。含有 GM3-αGalCer、(Neu5Gc)GM3-αGalCer 和等摩尔量的两种缀合物的脂质体已得到充分表征，并且它们激活 iNKT 细胞的能力已在小鼠和人类细胞测定中得到离体证实。这些候选药物在体内免疫研究中进行了测试，证明其能够诱导 T H 1 和 T H 2 细胞因子，从而产生 IgG 抗体的所有亚类。值得注意的是，该研究还表明，针对两种 TACA 的血清
• Synthesis of a spacer-armed disulfated tetrasaccharide of SB1a, a carbohydrate hapten associated with human hepatocellular carcinoma
  作者：Qin Li、Hui Li、Qing Li、Qing-Hua Lou、Bin Su、Meng-Shen Cai、Zhong-Jun Li

  DOI：10.1016/s0008-6215(02)00291-4

  日期：2002.11

  A disulfated tetrasaccharide fragment with a spacer arm of human hepatocellular carcinoma carbohydrate antigen SB1a, namely, 2-aminoethyl 3-O-sulfo-beta-D-galactopyranosyl-(1 --> 3)-2-acetamido-2-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-sulfo-beta-D-galactopyranosyl-(1 --> 4)-beta-D-glucopyranoside was synthesized via a [2 + 1 + 1] block building mode. In the last coupling step toward the trisaccharide acceptor 8, benzoyl protected galactosyl bromide donor 14 was found to be much more reactive than the acetyl-protected donors. (C) 2002 Elsevier Science Ltd. All rights reserved.
• 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.
• Synthesis of the Lewis b hexasaccharide and squarate acid–HSA conjugates thereof with various saccharide loadings
  作者：Anatoly Chernyak、Stefan Oscarson、Dominika Turek

  DOI：10.1016/s0008-6215(00)00189-0

  日期：2000.11

  alpha-L-Fucp-(1 --> 2)-beta-D-Galp-(1 --> 3)-[alpha-L-Fucp-(1 --> 4)]-beta-D-GlcpNAc-(1 --> 3)-beta-D-Galp-(l --> 4)-beta-D-Glcp, has been synthesised using a convergent synthesis. Starting from ethyl 4,6-O-benzylidene-2-deoxy-2-phthalimido-1-thio-beta-D-glucopyranoside, a thioglycoside tetrasaccharide donor block, was constructed through two orthogonal glycosylations with glycosyl bromide donors. First,

  Lewis b六糖，α-L-Fucp-（1-> 2）-β-D-Galp-（1-> 3）-[α-L-Fucp-（1-> 4）]-β -D-GlcpNAc-（1→3）-β-D-Galp-（1→4）-β-D-Glcp已经使用收敛合成法合成。从乙基4,6-O-亚苄基-2-脱氧-2-邻苯二甲酰亚胺-1-硫代-β-D-吡喃葡萄糖苷开始，通过与糖基溴化物供体的两次正交糖基化，构建了硫代糖苷四糖供体嵌段。首先，使用三氟甲磺酸银作为促进剂引入半乳糖部分，然后在卤化物辅助条件下引入两个岩藻糖残基。最后，将该四糖以DMTST促进的偶联方式连接到带有间隔基的3I，4I-二醇乳糖受体上，以在脱保护后得到带有2-氨基乙基间隔基的衍生物Lewis b六糖。这与人类血清白蛋白（HSA）偶联，