ethyl 2,3,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside | 213743-11-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside
• 英文别名: ethyl 2,3,6-tri-O-benzoyl-β-D-thio-galactopyranoside；[(2R,3S,4S,5R,6S)-4,5-dibenzoyloxy-6-ethylsulfanyl-3-hydroxyoxan-2-yl]methyl benzoate
• CAS: 213743-11-4
• 化学式: C₂₉H₂₈O₈S
• 分子量: 536.603
• InChiKey: IAOKJFAZDSOUDA-HGQALCJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  38
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  134
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside 在 2,4,6-三甲基吡啶 、 4 A molecular sieve 、 silver trifluoromethanesulfonate 、 DMTST 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 hexadecyl (3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-glucopyranosyl)-(1-4)-2,3,6-tri-O-benzoyl-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of Oligosaccharides Designed to form Micelles, Corresponding to Structures Found in Ovarian Cyst Fluid

  摘要：

  The syntheses of alpha-D-GlcpNAc-(1-->4)-beta-D-Galp-(1-->4)-beta-D-GlcNAc-(1-->O)-(CH2)(15)CH3 (1) and fragments thereof, corresponding to structures found in human ovarian cyst fluid, are described. Silver triflate promoted coupling of 3.4,6-tri-O-acetyl-2-azido-2-deoxy-beta-D-glucopyranosyl bromide (12) and galactose acceptor (11) gave a disaccharide donor (13), which was readily transformed into the corresponding bromo-derivative 18. For the synthesis of disaccharide beta-D-Galp-(1-->4)-D-GlcNAc, several differently protected glucosamine accepters were prepared. It was found that cetyl alcohol needed to be introduced after the formation of the P-galactoside bond. Glycosylation of pent-4-enyl 3,6-di-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (30) with (3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-glucopyranosyl)-(1-->4)-2,3,6-tri-O-benzoyl-alpha-D-galactopyranosyl bromide (18) by use of silver triflate as promoter gave the desired trisaccharide 31. Finally 31 was transformed via coupling to the long alkyl chain aglycon and deprotection into the title compound 1.

  DOI：

  10.1080/07328300008544063
• 作为产物：
  描述：

  1-硫代-Β-D-乙基半乳糖苷 在 吡啶 、 水 、 对甲苯磺酸 、 三乙胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.41h， 生成 ethyl 2,3,6-tri-O-benzoyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Chemical synthesis of globotriose and galabiose: relative stabilities of their complexes with Escherichia coli Shiga-like toxin-1 as determined by denaturation-titration with guanidinium chloride

  摘要：

  Globotriose [α-D-Gal-(1→4)-β-D-Gal-(1→4)-D-Glc] 是球三糖苷 (Gb3) 的碳水化合物部分，也称为生发中心 B 细胞分化抗原 CD77，是一种存在于某些哺乳动物细胞质膜上的糖脂。在 Gb3 中，球三糖作为志贺毒素和志贺样毒素（verocytotoxins）的细胞表面受体。这里我们报道了球三糖和相应的末端二糖，galabiose [α-D-Gal-(1→4)-β-D-Gal] 的化学合成。球三糖和 galabiose 通过一个连接子连接到 CNBr 活化的 Sepharose 上，生成亲和矩阵，允许从粗大肠杆菌匀浆中一步纯化重组志贺样毒素-1。毒素通过 6 M 胲盐酸盐洗脱从任一固定糖中释放出来。在稀释变性剂后，释放的毒素具有完全的催化活性。变性滴定实验显示，结合在 galabiose-Sepharose 上的毒素在 2.3 M 胲盐酸盐下释放，而从 globotriose-Sepharose 上释放需要更高的 4.8 M 浓度。这些结果表明，球三糖的葡萄糖成分相对于 galabiose，对结合能的贡献约为 2.6 kcal mol–1。

  DOI：

  10.1039/a801429i

文献信息

• Chemical synthesis of globotriose and galabiose: relative stabilities of their complexes with Escherichia coli Shiga-like toxin-1 as determined by denaturation-titration with guanidinium chloride
  作者：Dieter Müller、Gabin Vic、Peter Critchley、David H. G. Crout、Nicholas Lea、Lynne Roberts、J. Michael Lord

  DOI：10.1039/a801429i

  日期：——

  Globotriose [α-D-Gal-(1→4)-β-D-Gal-(1→4)-D-Glc] is the carbohydrate moiety of the globotriosyl ceramide (Gb3), also known as the germinal centre B-cell differentiation antigen CD77, a glycolipid present on the plasma membrane of certain mammalian cells. In Gb3, globotriose functions as the cell-surface receptor for Shiga toxin and for the Shiga-like toxins (verocytotoxins). Here we report the chemical synthesis of globotriose and the corresponding terminal disaccharide, galabiose [α-D-Gal-(1→4)-β-D-Gal]. Globotriose and galabiose are attached via a linker to CNBr-activated Sepharose to generate affinity matrices that permit the one-step purification of recombinant Shiga-like toxin-1 from crude E. coli homogenates. Toxin is released from either of the immobilised saccharides by elution with 6 M guanidinium chloride. After dilution of the denaturant, the released toxin had full catalytic activity. Denaturation-titration experiments show that the bound toxin is released from galabiose-Sepharose at 2.3 M guanidinium chloride, while its release from globotriose-Sepharose requires a higher concentration of 4.8 M. These results indicate that the glucose component of globotriose contributes ≈2.6 kcal mol–1 to the binding energy relative to galabiose.

  Globotriose [α-D-Gal-(1→4)-β-D-Gal-(1→4)-D-Glc] 是球三糖苷 (Gb3) 的碳水化合物部分，也称为生发中心 B 细胞分化抗原 CD77，是一种存在于某些哺乳动物细胞质膜上的糖脂。在 Gb3 中，球三糖作为志贺毒素和志贺样毒素（verocytotoxins）的细胞表面受体。这里我们报道了球三糖和相应的末端二糖，galabiose [α-D-Gal-(1→4)-β-D-Gal] 的化学合成。球三糖和 galabiose 通过一个连接子连接到 CNBr 活化的 Sepharose 上，生成亲和矩阵，允许从粗大肠杆菌匀浆中一步纯化重组志贺样毒素-1。毒素通过 6 M 胲盐酸盐洗脱从任一固定糖中释放出来。在稀释变性剂后，释放的毒素具有完全的催化活性。变性滴定实验显示，结合在 galabiose-Sepharose 上的毒素在 2.3 M 胲盐酸盐下释放，而从 globotriose-Sepharose 上释放需要更高的 4.8 M 浓度。这些结果表明，球三糖的葡萄糖成分相对于 galabiose，对结合能的贡献约为 2.6 kcal mol–1。
• Synthesis of tri-, penta-, and heptasaccharides, functionalized with orthogonally N-protected amino residues at the reducing and non-reducing ends
  作者：Timmy Fyrner、Stefan C.T. Svensson、Peter Konradsson

  DOI：10.1016/j.tet.2012.05.118

  日期：2012.8

  N-Boc-protected glycine moiety, and further connected to either a mannose (1→6) disaccharide or (1→3) lactose units (one, two or three) resulting in tri-, penta-, or heptasaccharides. All of the synthesized oligosaccharides have an N-benzyloxycarbonyl-aminoethyl residue at the reducing end. The orthogonal N-Boc/N-Cbz protection group pattern enables further conjugation/derivatization and results in a hydrophilic

  描述了意欲作为交联衍生物的衍生自乳糖和甘露糖的四种双官能化的正交N-保护的寡糖的合成。非还原端的氨基糖被N -Boc保护的甘氨酸部分衍生化，并进一步连接至甘露糖（1→6）二糖或（1→3）乳糖单元（1、2或3），得到三糖，五糖或七糖。所有合成的寡糖在还原端均具有N-苄氧基羰基-氨基乙基残基。正交N -Boc / N-Cbz保护基图案可实现进一步的共轭/衍生化，并产生亲水性交联分子。发现最终合成步骤的顺序对于避免酰基迁移至关重要。已经应用合适的酰胺偶联方案以将N -Boc保护的甘氨酸部分引入醇溶剂中。合成的低聚糖将提供一个模型系统来研究长度，结构和柔韧性的影响。
• Chemoselective glycosylations of sterically hindered glycosyl acceptors
  作者：Richard Geurtsen、Geert-Jan Boons

  DOI：10.1016/s0040-4039(02)02334-1

  日期：2002.12

  Unexpected intermolecular aglycon transfer in chemoselective glycosylations between activated thioglycosyl donors and deactivated thioglycosyl acceptors could be avoided by employing a glycosyl acceptor that has a bulky anomeric dicyclohexylmethanethio group. The methodology was applied to the synthesis of a protected fragment of an oligosaccharide released from the jelly coat glycoprotein of X. leavis

  通过使用具有庞大的异头二环己基甲硫基的糖基受体，可以避免活化的硫糖基供体和失活的硫糖基受体之间在化学选择性糖基化过程中发生意外的分子间糖苷配基转移。该方法适用于从X.leavis的果冻外壳糖蛋白释放的保护寡糖片段的合成。
• Synthesis of Oligosaccharides Designed to form Micelles, Corresponding to Structures Found in Ovarian Cyst Fluid
  作者：Therese Buskas、Peter Konradsson

  DOI：10.1080/07328300008544063

  日期：2000.1

  The syntheses of alpha-D-GlcpNAc-(1-->4)-beta-D-Galp-(1-->4)-beta-D-GlcNAc-(1-->O)-(CH2)(15)CH3 (1) and fragments thereof, corresponding to structures found in human ovarian cyst fluid, are described. Silver triflate promoted coupling of 3.4,6-tri-O-acetyl-2-azido-2-deoxy-beta-D-glucopyranosyl bromide (12) and galactose acceptor (11) gave a disaccharide donor (13), which was readily transformed into the corresponding bromo-derivative 18. For the synthesis of disaccharide beta-D-Galp-(1-->4)-D-GlcNAc, several differently protected glucosamine accepters were prepared. It was found that cetyl alcohol needed to be introduced after the formation of the P-galactoside bond. Glycosylation of pent-4-enyl 3,6-di-O-benzyl-2-deoxy-2-tetrachlorophthalimido-beta-D-glucopyranoside (30) with (3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-glucopyranosyl)-(1-->4)-2,3,6-tri-O-benzoyl-alpha-D-galactopyranosyl bromide (18) by use of silver triflate as promoter gave the desired trisaccharide 31. Finally 31 was transformed via coupling to the long alkyl chain aglycon and deprotection into the title compound 1.
• Synthesis of galactoglycerolipids found in the HT29 human colon carcinoma cell line
  作者：Jan Lindberg、Stefan C.T Svensson、Peter Påhlsson、Peter Konradsson

  DOI：10.1016/s0040-4020(02)00473-8

  日期：2002.6

  Synthesis of three galactoglycerolipids (3-O-(beta-D-galactopyranosyl)-1-O-hexadecyl-2-O-palmitoyl-sn-glycerol, 3-O-(alpha-D-galactopyranosyl-(1-->4)-beta-D-galactopyranosyl)-1-O-hexadecyl-2-O-palmitoyl-sn-glycerol, 3-O-(alpha-D-galactopyranosyl-(1-->4)-beta-D-galactopyranosyl)-1-O-hexadecyl-sn-glycerol), and the corresponding glycerolipid (1-O-hexadecyl-2-O-palmitoyl-sn-glycerol) is described. The first two compounds were recently identified in the human colon carcinoma cell line HT29. The three-carbon synthon (S)-glycidol was used for construction of the glycerol moiety. Glycosylation of (S)-glycidol with protected galactosyl and digalactosyl donors produced galactosyl and digalactosyl glycidols. Lewis acid catalyzed opening of the epoxide produced protected galactosyl and digalactosyl glycerolipids. Deprotection, or palmitoylation followed by deprotection, yielded the target compounds. The corresponding glycerolipid was synthesized analogously and an oxidation-reduction procedure for tritiation was developed. The synthesized compounds will be used in studies of the role of galactosyl glycerolipids in differentiation and colon cancer development. (C) 2002 Elsevier Science Ltd. All rights reserved.