p-tolyl 3,5-O-(di-tert-butylsilanediyl)-1-thio-α-D-arabinofuranoside | 917590-98-8

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: p-tolyl 3,5-O-(di-tert-butylsilanediyl)-1-thio-α-D-arabinofuranoside
• 英文别名: p-cresyl 3,5-O-(di-tert-butylsilylene)-1-thio-α-D-arabinofuranoside；p-tolyl 3,5-O-(di-tert-butylsilylene)-1-thio-α-D-arabinofuranoside
• CAS: 917590-98-8
• 化学式: C₂₀H₃₂O₄SSi
• 分子量: 396.623
• InChiKey: GTZAMLUGBPWDLX-XMTFNYHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.63
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  47.92
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  p-tolyl 3,5-O-(di-tert-butylsilanediyl)-1-thio-α-D-arabinofuranoside 在 2,6-二甲基吡啶 、 N-碘代丁二酰亚胺 、 3 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 benzyl 3,5-O-(di-tert-butylsilylene)-2-O-triisopropylsilyl-α-D-arabinofuranosyl-(1->2)-3,5-O-dibenzyl-α-D-arabinofuranoside
  参考文献：
  名称：

  Stereoselective Synthesis of a Fragment of Mycobacterial Arabinan

  摘要：

  Strategies for the stereoselective synthesis of mycobacterial arabinan were explored. Arabinofuranosyl donors with various protective groups were screened in terms of suitability for beta-( 1,2- cis)- selective glycosylation. The protective group was found to affect the stereoselectivity of arabinofuranosylation. beta-Selectivity was drastically enhanced by using donors protected with 3,5- TIDPS, possibly due to conformational constraints on the furanose ring. Synthesis of heptaarabinofuranoside was then performed to demonstrate the practicality of this methodology.

  DOI：

  10.1021/ol062198j
• 作为产物：
  描述：

  4-甲苯硫酚 在 吡啶 、 4-二甲氨基吡啶 、 三氟化硼乙醚 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 12.0h， 生成 p-tolyl 3,5-O-(di-tert-butylsilanediyl)-1-thio-α-D-arabinofuranoside
  参考文献：
  名称：

  对使用3,5- Ø亚苄基和3,5- Ö - （二-叔-butylsilylene）-2- Ø -benzylarabinothiofuranosides及其亚砜作为糖基供体的β阿拉伯呋喃糖苷的合成：激活方法的重要性

  摘要：

  A 2- ø -苄基-3,5- ø -亚苄基- α- d -thioarabinofuranoside通过在碱性条件下α，α-二溴甲苯相应二醇的反应来获得。在-55°C下用1-苯亚磺酰基哌啶或二苯亚砜和三氟甲磺酸酐在二氯甲烷中活化后，与糖基受体的反应可提供极少或没有选择性的异头混合物。在1-苯亚磺酰基哌啶或二苯基亚砜条件下，类似的2 - O-苄基-3,5 - O-（二叔丁基亚甲硅烷基）-α- d-硫代阿拉伯呋喃糖苷也没有显示出明显的选择性。与N-碘代琥珀酰亚胺和三氟甲磺酸银表明，甲硅烷基乙缩醛具有中等至高的β-选择性，而与起始硫代糖苷的构型无关。用三氟甲磺酸酐活化后的2 - O-苄基-3,5 - O-（二叔丁基亚甲硅烷基）-α-阿拉伯呋喃糖基亚砜供体也获得了高β-选择性。N获得的高β选择性-碘代琥珀酰亚胺/三氟甲磺酸银和亚砜的方法与常见的中间体一致，最有可能是氧杂碳鎓离子。用1-苯亚磺酰基

  DOI：

  10.1021/jo061440x

文献信息

• Efficient one-pot syntheses of α-d-arabinofuranosyl tri- and tetrasaccharides present in cell wall polysaccharide of Mycobacterium tuberculosis
  作者：Xing-Yong Liang、Li-Min Deng、Xia Liu、Jin-Song Yang

  DOI：10.1016/j.tet.2009.11.038

  日期：2010.1

  Two alpha-D-arabinofuramosyl oligosaccharides (2 and 3) found as constituent parts of the polysaccharide portion from the cell wall of Mycobacterium tuberculosis have been efficiently synthesized via a one-pot glycosylation procedure in which a key step is the chemoselective activation between D-arabinofuranosyl trichloroacetimidate donor 4 and partially protected aryl thioglycosides 5 or 7, respectively. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis of the Docosanasaccharide Arabinan Domain of Mycobacterial Arabinogalactan and a Proposed Octadecasaccharide Biosynthetic Precursor
  作者：Maju Joe、Yu Bai、Ruel C. Nacario、Todd L. Lowary

  DOI：10.1021/ja072892+

  日期：2007.8.1

  Two major components of the cell wall in mycobacteria, including Mycobacterium tuberculosis, the causative agent of tuberculosis (TB), are polysaccharides containing arabinofuranose residues. In one of these polysaccharides, arabinogalactan, this arabinan domain consists of three identical motifs of 22 arabinofuranose residues, which are in turn attached to an underlying galactofuranan backbone. Recent studies have proposed that this docosanasaccharide motif, and a structurally related arabinan present in another cell wall polysaccharide, lipoarabinomannan, are biosynthesized from a common octadecasaccharide precursor. To facilitate the testing of this hypothesis, we report here the first total syntheses of these 18- and 22-residue oligosaccharides both functionalized with an aminooctyl linker arm. The route to the target compounds involved the preparation of four tri- to heptasaccharide building blocks possessing only benzoyl protecting groups that were coupled in a highly convergent manner via glycosyl trichloroacetimidate donors. Each of the targets could be prepared in only six steps from these intermediates, and in both cases more than 10 mg of material was obtained. These compounds are expected to be useful tools in probing the biosynthesis of these arabinan-containing polysaccharides. Such studies are essential prerequisites for the identification of novel anti-TB agents that target arabinan assembly.
• Ligand Specificity of CS-35, a Monoclonal Antibody That Recognizes Mycobacterial Lipoarabinomannan:  A Model System for Oligofuranoside−Protein Recognition
  作者：Christoph Rademacher、Glen K. Shoemaker、Hyo-Sun Kim、Ruixiang Blake Zheng、Hashem Taha、Chunjuan Liu、Ruel C. Nacario、David C. Schriemer、John S. Klassen、Thomas Peters、Todd L. Lowary

  DOI：10.1021/ja0723380

  日期：2007.8.1

  The CS-35 antibody is widely used in the characterization of glycans containing D-arabinofuranose residues, in particular polysaccharides present in the mycobacterial cell wall. A detailed understanding of the combining site of this antibody and the measurement of its binding to different ligands is of interest as this knowledge will have implications in the characterization of arabinofuranose-containing glycoconjugates that are increasingly recognized as important biological molecules. Of even greater significance is that an in-depth study of this carbohydrate-protein interaction will provide insights into the mechanisms by which oligosaccharides containing furanose rings are bound by proteins, an area that has, to date, received little attention. This system has been refractory to X-ray crystallography, and thus we report here a study of the interaction of CS-35 with its ligands using a combination of chemical synthesis, mass spectrometry, titration microcalorimetry, and NMR spectroscopy. Through these investigations we have established that the binding pocket recognizes, as a minimum epitope, a linear tetrasaccharide motif and that the residues at the reducing and non-reducing end of the oligosaccharide are essential for tight binding. The residue at the non-reducing end appears to be bound in an aliphatic pocket, whereas the rest of the tetrasaccharide interacts more strongly with aromatic amino acids.