2,3-di-O-benzoyl-1-ethylthio-β-D-galactopyranoside | 154391-05-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-di-O-benzoyl-1-ethylthio-β-D-galactopyranoside
• 英文别名: (2S,3R,4S,5S,6R)-2-(Ethylthio)-5-hydroxy-6-(hydroxymethyl)tetrahydro-2H-pyran-3,4-diyl dibenzoate；[(2S,3R,4S,5S,6R)-3-benzoyloxy-2-ethylsulfanyl-5-hydroxy-6-(hydroxymethyl)oxan-4-yl] benzoate
• CAS: 154391-05-6
• 化学式: C₂₂H₂₄O₇S
• 分子量: 432.494
• InChiKey: YLPJYVKVAZFIOM-IHZGOTPNSA-N

物化性质

• 沸点：
  635.7±55.0 °C(Predicted)
• 密度：
  1.35±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  128
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2,3-di-O-benzoyl-1-ethylthio-β-D-galactopyranoside 在 吡啶 、 2,3,5-三甲基吡啶 、 4 A molecular sieve 、 sodium methylate 、 sodium hydride 、 DMTST 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.0h， 生成 (R)-glycidyl 2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of galactoglycerolipids found in the HT29 human colon carcinoma cell line

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(02)00473-8
• 作为产物：
  描述：

  ethyl 2,3-di-O-benzoyl-4,6-O-benzylidene-1-thio-β-D-galactopyranoside 在 三氟乙酸 作用下， 以 二氯甲烷 、 乙二醇 为溶剂， 反应 1.0h， 生成 2,3-di-O-benzoyl-1-ethylthio-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of galactoglycerolipids found in the HT29 human colon carcinoma cell line

  摘要：

  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.

  DOI：

  10.1016/s0040-4020(02)00473-8

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。
• C-5 Modified S-Benzoxazolyl Sialyl Donors: Towards More Efficient Selective Sialylations
  作者：Benjamin N. Harris、Payal P. Patel、Chase P. Gobble、Matthew J. Stark、Cristina De Meo

  DOI：10.1002/ejoc.201100539

  日期：2011.7

  We previously reported that the selective activation of an S-benzoxazolyl (SBox) sialyl donor over a galactosyl acceptor equipped with a thioethyl anomeric moiety can be performed in high yield but with poor stereoselectivity. To optimize this strategy, which allows the synthesis of complex carbohydrates to be shortened, a range of SBox sialyl donors modified at C-5 were synthesized and tested. In

  我们之前报道过 S-苯并恶唑基 (SBox) 唾液酸供体在配备有硫乙基异头部分的半乳糖基受体上的选择性活化可以以高产率进行，但立体选择性较差。为了优化这一策略，缩短复杂碳水化合物的合成，合成并测试了一系列在 C-5 处修饰的 SBox 唾液酸供体。特别是，SBox 离去基团和 C-4,5 的恶唑烷酮的组合​​允许在各种溶剂和不同温度下实现出色的立体控制。在二氯甲烷/四氢呋喃 (1:1) 溶剂系统中，在三氟甲磺酸铋 (III) 存在下获得了几乎完全的立体选择性。
• Synthesis of 5-aminopentyl 4,6-O-[(R)-1-carboxyethylidene]-β-d-galactopyranoside and its use as a ligand for the affinity chromatography of human serum amyloid P protein
  作者：Thomas Ziegler、Elisabeth Eckhardt、Jochen Strayle、Helmut Herzog

  DOI：10.1016/0008-6215(94)80063-4

  日期：1994.2

  corresponding protected beta-D-galactoside 27, deblocking of which afforded the title compound 1. Binding of 1 to epoxypropyl-modified acrylamide beads gave an affinity adsorbent that was used to isolate serum amyloid P protein from human serum.

  一系列2,3-二-O-苯甲酰基-D-吡喃半乳糖苷，α-烯丙基（5），α-苄基（6），β-乙基-1-硫代（7），β-苯基-1-硫代（由相应的4，6-O-亚苄基衍生物制备8）和α-甲基（9），并用丙酮酸甲酯在乙腈中缩醛化，以非对映选择性得到2,3-二-O-苯甲酰基-4,6。 -O-[（R）-1-甲氧基羰基亚乙基] -D-吡喃半乳糖苷10-16。将后者转化为2，3-二-O-苯甲酰基-4，6-O-[（R）-1-甲氧基羰基亚乙基] -D-半乳糖吡喃糖基α-和β-三氯乙亚氨酸酯19和20，α-和β -氟化物21和22，α-溴化物23和α-氯化物24。这些供体（包括苯基1-硫代半乳糖苷14）与5-[（苄氧基羰基）氨基]戊醇反应，得到相应的受保护的β-D-半乳糖苷27，
• A Ring Contraction of 2,3-Di-<i>O</i>-Silylated Thiopyranosides To Give Thiofuranosides under Mildly Acidic Conditions
  作者：Polina I. Abronina、Nelly N. Malysheva、Veronika V. Litvinenko、Alexander I. Zinin、Natalya G. Kolotyrkina、Leonid O. Kononov

  DOI：10.1021/acs.orglett.8b02424

  日期：2018.10.5

  with acid-labile protective groups at O-4 will also engage in this reaction). The rearrangement cleanly proceeds for 2,3-di-O-TIPS derivatives with two hydroxy groups at C-4 and C-6, acid-labile TES groups at O-4 and O-6, or one acyl substituent (Bz, ClAc) at O-6. A possibility to switch the direction of the debenzylidenation reaction in 4,6-O-benzylidene-2,3-di-O-TIPS/TBDPS derivatives by the choice

  已经发现乙基1-硫代-β- d-吡喃半乳糖苷的吡喃糖环收缩在中等酸性条件下（CH 2 Cl 2中的TFA水溶液）保留了糖苷配基。这种重排成功的关键因素是在O-2和O-3处均存在庞大的甲硅烷基（TIPS或TBDPS）取代基，在C-4处存在游离羟基（在O-4处具有酸不稳定保护基的衍生物会也参与这个反应）。2,3-二-重排干净地进行ö在C-4和C-6 -提示与两个羟基的衍生物，在O-4和O-6，或一个酰基取代基（BZ，CLAC酸不稳定基团TES ）在O-6。可以在4,6- O中切换脱苄基反应的方向通过选择一种酸（TFA，可干净地生成呋喃糖，而AcOH，仅可裂解亚苄基乙缩醛）选择-苄基-2,3-二-O - TIPS / TBDPS衍生物，在选择性保护糖基的发散合成中可能具有优势供体（呋喃糖或吡喃糖形式）可用于合成生物学上重要的低聚糖。
• Thiomidoyl approach to the synthesis of α-sialosides
  作者：Cristina De Meo、Olivia Parker

  DOI：10.1016/j.tetasy.2004.11.043

  日期：2005.1

  Novel sialosyl donors, S-benzoxazolyl (SBox) and S-thiazolyl (STaz) sialosides, have been synthesized and applied to the stereoselective synthesis of alpha-sialosides. It was also demonstrated that it is possible to selectively activate SBox sialyl donor over ethyl thioglycoside, allowing the direct synthesis of disaccharide donors that could be used in subsequent glycosylations without further manipulations. (C) 2004 Elsevier Ltd. All rights reserved.