ethyl-3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamido)-1-thio-β-D-glucopyranoside | 169557-88-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl-3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamido)-1-thio-β-D-glucopyranoside
• 英文别名: ethyl 3,4,6-tri-O-acetyl-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside；ethyl 3,4,6-tri-O-acetyl-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside；[(2R,3S,4R,5R,6S)-3,4-diacetyloxy-6-ethylsulfanyl-5-[(2,2,2-trichloroacetyl)amino]oxan-2-yl]methyl acetate
• CAS: 169557-88-4
• 化学式: C₁₆H₂₂Cl₃NO₈S
• 分子量: 494.778
• InChiKey: HZHQPKBSQONDHT-KSTCHIGDSA-N

物化性质

• 熔点：
  133-134 °C
• 沸点：
  568.7±50.0 °C(Predicted)
• 密度：
  1.43±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  143
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  ethyl-3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamido)-1-thio-β-D-glucopyranoside 在 三氟甲磺酸三甲基硅酯 、 四丁基氟化铵 、 sodium methylate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 54.33h， 生成 methyl 2-O-benzoyl-4,6-di-O-benzylidene-α-D-glucopyranoside
  参考文献：
  名称：

  TMSOTf 催化的甲硅烷基化：简化的区域选择性一锅保护和碳水化合物的乙酰化

  摘要：

  已经开发出一种高效的 TMSOTf 催化的 HMDS 糖基硅烷化，它可以很容易地以一锅法与后续反应相结合。其在简化区域选择性一锅法保护和非酶乙酰化方面的应用证明了其有用性。

  DOI：

  10.1002/ejoc.201101267
• 作为产物：
  描述：

  2-氨基-2-脱氧葡萄糖盐酸盐 在 吡啶 、 三氟化硼乙醚 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 147.0h， 生成 ethyl-3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamido)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  硫酸皮肤素寡糖的模块化自动固相合成。

  摘要：

  硫酸皮肤素是糖胺聚糖多糖，其作为细胞外基质的一部分具有多种生物学作用。正交保护的D-半乳糖胺和L-艾杜糖醛酸结构单元以及可光裂解的接头对于硫酸皮肤素寡糖的自动合成至关重要。以高收率获得了易于结合的寡糖。

  DOI：

  10.1039/c3cc48860h

文献信息

• Efficient Synthesis of Two HNK-1 Related Pentasaccharides
  作者：Ole Hindsgaul、Frederic Belot、Albin Otter、Minoru Fukuda

  DOI：10.1055/s-2003-40324

  日期：——

  Two pentasaccharides, representative of those found on complex N-glycans, were synthesized for use as potential substrates for sulfotransferases. The synthesis was achieved by the addition of a disaccharide donor β-D-GlcA(1→3)α-D-Gal-trichloroacetimidate to the two acceptor trisaccharides β-D-GlcNAc( 1→6)α-D-Man(1→6)β-D-Man-O-octyl (15) and β-D-GlcNAc(1→2α-D-Man(1→6)β-D-Man-O-octyl (14). After deprotection

  合成了两种五糖，代表在复杂 N-聚糖上发现的那些，用作磺基转移酶的潜在底物。该合成是通过将二糖供体 β-D-GlcA(1→3)α-D-Gal-三氯乙酰亚胺添加到两个受体三糖 β-D-GlcNAc(1→6)α-D-Man(1) 中实现的→6)β-D-Man-O-辛基(15)和β-D-GlcNAc(1→2α-D-Man(1→6)β-D-Man-O-辛基(14)。脱保护后，两种五糖 1 和 2 通过 1 H NMR 光谱表征。
• The synthesis of linear trilactosamine
  作者：G. V. Pazynina、V. V. Severov、N. V. Bovin

  DOI：10.1134/s1068162008050129

  日期：2008.9

  TrilactosamineGal beta 1-4GlcNAc beta 1-3Gal beta 1-4GlcNAc beta 1-3Gal beta 1-4GlcNAc beta-sp, where sp = O(CH(2))(3)NH(2) is a spacer, was synthesized. The tetrasaccharide fragment Gal beta 1-4GlcNAc beta 1-3Gal beta 1-4GlcNAc beta-sp was obtained by successive glycosylation using elongation by one monosaccharide residue at a time; and the tetrasaccharide was then transformed into a hexasaccharide with a disaccharide glycosyl donor. A 2,2,2-trichloroethoxycarbonyl group was used for the protection of the glucosamine amino group.
• Study of glycosylation with N-trichloroacetyl-d-glucosamine derivatives in the syntheses of the spacer-armed pentasaccharides sialyl lacto-N-neotetraose and sialyl lacto-N-tetraose, their fragments, and analogues
  作者：Andrei A. Sherman、Olga N. Yudina、Yury V. Mironov、Elena V. Sukhova、Alexander S. Shashkov、Vladimir M. Menshov、Nikolay E. Nifantiev

  DOI：10.1016/s0008-6215(01)00213-0

  日期：2001.11

  The syntheses of 2-aminoethyl glycosides of the pentasaccharides Neu5Ac-alpha (2 --> 3)-Gal-beta (3(1 --> 4)-GlcNAc-beta (3(1 --> 3)-Gal-beta (1 --> 4)-Glc and Neu5Ac-alpha (2 --> 3)-Gal-beta (1 --> 3)-GlcNAc-beta (1 --> 3)-Gal-beta (1 --> 4)-Glc, their asialo di-, tri-, and tetrasaccharide fragments, and analogues included a systematic study of glycosylation with variously protected mono- and disaccharide donors derived from N-trichloroacetyl-D-glucosamine of galactose, lactose, and lactosamine glycosyl acceptors bearing benzoyl protection around the OH group to be glycosylated. Despite the. low reactivity of these acceptors, stereo specificity and good to excellent yields were obtained with NIS-TfOH-activated thioglycoside donors of such type, or with AgOTf-activated glycosyl bromides, while other promotors, as well as a trichloroacetimidate donor, were less effective, and a beta -acetate donor was inactive. In NIS-TfOH-promoted glycosylation with the thioglycosides, the use of TfOH in catalytic amount led to rapid formation of the corresponding oxazoline, but the quantity of TfOH necessary for further efficient coupling with an acceptor depended on the reactivity of the donor, varying from 0.07 equiv for a 3,6-di-O-benzylated monosaccharide derivative to 2.1 equiv for a peracetylated disaccharide one. In the glycosylation products, the N-trichloroacetyl group was easily converted into N-acetyl by alkaline hydrolysis followed by N-acetylation. (C) 2001 Elsevier Science Ltd. All rights reserved.
• Coutant, Caroline; Jacquinet, Jean-Claude, Journal of the Chemical Society. Perkin transactions I, 1995, # 12, p. 1573 - 1582
  作者：Coutant, Caroline、Jacquinet, Jean-Claude

  DOI：——

  日期：——
• Practical Synthesis of Building Blocks for Oligosaccharides Containing the β-d-Galp-(1→3)-β-d-GlcpNAc Motif
  作者：Pavol Kováč、Sameh Soliman

  DOI：10.1055/s-0033-1340620

  日期：——

  An efficient, new pathway for the synthesis of the title sequence has been developed. The sequence has been obtained as a glycosyl donor, beta-D-Galp-(1 -> 3)-beta-D-GlcpNAc-1-SEt, or equipped with a linker (spacer) suitable for conjugation to other molecules, beta-D-Galp-(1 -> 3)-beta-D-GlcpNAc-1-(OCH2CH2)(3)N-3. Both disaccharides have been obtained in crystalline condition for the first time and fully characterized. The existing synthesis of the intermediate disaccharide glycosyl donor was improved by conducting the silver triflate mediated glycosylation under base-deficient conditions in the presence of 1,1,3,3-tetramethylurea and in the absence of molecular sieves.