p-cresyl 2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl-1-thio-α-D-arabinofuranoside | 204918-56-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: p-cresyl 2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl-1-thio-α-D-arabinofuranoside
• 英文别名: p-tolyl 5-O-tert-butyldiphenylsilyl-2,3-di-O-benzoyl-1-thio-α-D-arabinofuranoside；p-cresyl 2,3-di-O-benzoyl-5-O-t-butyldiphenylsilyl-1-thio-α-D-arabinofuranoside；2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl-1-(4-methylphenylthio)-α-D-Araf；[(2R,3R,4S,5R)-4-benzoyloxy-2-[[tert-butyl(diphenyl)silyl]oxymethyl]-5-(4-methylphenyl)sulfanyloxolan-3-yl] benzoate
• CAS: 204918-56-9
• 化学式: C₄₂H₄₂O₆SSi
• 分子量: 702.943
• InChiKey: PEMJUEGQNBSMCT-YMBHCLMJSA-N

物化性质

• 沸点：
  737.6±60.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.84
• 重原子数：
  50
• 可旋转键数：
  14
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  96.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  p-cresyl 2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl-1-thio-α-D-arabinofuranoside 在 N-碘代丁二酰亚胺 、 水 、 silver trifluoromethanesulfonate 作用下， 以 四氢呋喃 为溶剂， 反应 3.5h， 以85%的产率得到2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl D-arabinofuranose
  参考文献：
  名称：

  Synthesis of the Docosanasaccharide Arabinan Domain of Mycobacterial Arabinogalactan and a Proposed Octadecasaccharide Biosynthetic Precursor

  摘要：

  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.

  DOI：

  10.1021/ja072892+
• 作为产物：
  描述：

  1-(p-thiocresyl)-2,3,5-tri-O-acetyl-α-D-arabinofuranoside 在 吡啶 、 甲醇 、 sodium methylate 作用下， 生成 p-cresyl 2,3-di-O-benzoyl-5-O-tert-butyldiphenylsilyl-1-thio-α-D-arabinofuranoside
  参考文献：
  名称：

  Synthetic arabinofuranosyl oligosaccharides as Mycobacterial arabinosyltransferase substrates

  摘要：

  A series of arabinofuranosyl oligosaccharides found as constituent parts of the polysaccharide portion of the cell wall of Mycobacterium tuberculosis have been chemically synthesized. Screening of these oligosaccharides as substrates for arabinosyltransferases present in mycobacterial membrane preparations suggests that modified oligosaccharide analogs as small as disaccharides may be inhibitors of glycan biosynthesis. Such inhibitors would be of potential utility as lead compounds in the identification of new drugs for the treatment of mycobacterial infections. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(98)00049-3

文献信息

• Preparation of the tri-arabino di-mycolate fragment of mycobacterial arabinogalactan from defined synthetic mycolic acids
  作者：Mohsin O. Mohammed、Juma'a R. Al Dulayymi、Mark S. Baird

  DOI：10.1016/j.carres.2016.11.006

  日期：2017.1

  An efficient synthetic approach to tri-arabino di-mycolates, using structurally defined synthetic alpha-, keto and methoxy mycolic acids is described.

  描述了一种有效的合成方法，使用结构上定义的合成α-，酮和甲氧基霉菌酸合成三阿拉伯糖基二霉菌酸酯。
• Genetically-encoded fragment-based discovery (GE-FBD) of glycopeptide ligands with differential selectivity for antibodies related to mycobacterial infections
  作者：Ying Chou、Elena N. Kitova、Maju Joe、Richard Brunton、Todd L. Lowary、John S. Klassen、Ratmir Derda

  DOI：10.1039/c7ob02783d

  日期：——

  Accurate identification of tuberculosis (TB), caused by Mycobacterium tuberculosis, is important for global disease management. Point-of-care serological tests may improve TB diagnosis; however, specificities of available serodiagnostics are sub-optimal. We employed genetically encoded fragment-based discovery (GE-FBD) to select ligands for antibodies directed against the mycobacterial cell wall component

  由结核分枝杆菌引起的结核病（TB）的准确识别对于全球疾病管理非常重要。现场护理血清学检查可以改善结核病的诊断；但是，可用血清学诊断的特异性欠佳。我们采用基因编码的基于片段的发现（GE-FBD）为针对分枝杆菌细胞壁成分lipoarabinomannan（LAM）（一种有效的抗原）的抗体选择配体。GE-FBD使用了10个8个七肽的噬菌体展示文库，并用LAM的阿拉伯呋喃糖基六糖片段进行了化学修饰（Ara 6）和抗LAM抗体CS-35作为诱饵。该选择产生了对CS-35具有增强的亲和力和选择性但对906.4321抗体不具有亲和力和选择性的糖肽，两者均以相当的亲和力结合Ara 6。掺入发现的配体Ara 6 -ANSSFAP，Ara 6 -DAHATLR和Ara 6 -TTYVVNP的多价测定法在CS-35和906.4321之间显示出高达19倍的区分度。单独使用Ara 6抗原无法区分这些抗体。因此，GE
• Neighboring-Group Participation by C-2 Ether Functions in Glycosylations Directed by Nitrile Solvents
  作者：Chin-Sheng Chao、Ching-Yu Lin、Shaheen Mulani、Wei-Cheng Hung、Kwok-kong Tony Mong

  DOI：10.1002/chem.201100732

  日期：2011.10.17

  Ether‐protecting functions at C‐2 hydroxy groups have been found to play participating roles in glycosylations when the reactions are conducted in nitrile solvent mixtures. The participation mechanism is based on intramolecular interaction between the lone electron pair of the oxygen atom of the C‐2 ether function and the nitrile molecule when they are positioned in a cis configuration. A 1,2‐cis glycosyl

  当在腈溶剂混合物中进行反应时，已发现在C-2羟基处的醚保护功能在糖基化中起参与作用。参与机制基于C-2醚功能的氧原子的孤电子对和腈分子以顺式排列时的分子内相互作用。形成一个1,2-顺式糖基恶唑啉鎓中间体。这种参与，再加上糖基供体的异头作用，赋予糖基化较高的1,2-反式选择性。该概念的进一步应用导致了α-（1→5）-阿拉伯低聚物的高效制备。
• Synthesis of a Di-Mycoloyl Tri-Arabinofuranosyl Glycerol Fragment of the Mycobacterial Cell Wall, Based on Synthetic Mycolic Acids
  作者：Ali、Mohammed、Dulayymi、Baird

  DOI：10.3390/molecules24193596

  日期：——

  Fragments of mycobacterial cell walls such as arabinoglycerol mycolate and dimycoloyl diarabinoglycerol, comprising complex mixtures of mycolic acids, have immunostimulatory and antigenic properties. A related di-mycoloyl tri-arabinofuranosyl glycerol fragment has been isolated from cell wall hydrolysates. An effective stereoselective synthesis of tri-arabinofuranosyl glycerol, followed by coupling

  分枝杆菌细胞壁的片段，例如霉菌酸阿拉伯甘油酯和二霉菌酰二阿拉伯甘油酯，包含霉菌酸的复杂混合物，具有免疫刺激和抗原特性。已从细胞壁水解产物中分离出相关的二霉菌酰基三阿拉伯呋喃糖基甘油片段。现在描述了三阿拉伯呋喃糖基甘油的有效立体选择性合成，然后与立体化学定义的不同结构类别的霉菌酸偶联，以提供独特的二霉菌酰基三阿拉伯呋喃糖基甘油。
• Sensitivity of ¹<i>J</i>_C1_-_H1 Magnitudes to Anomeric Stereochemistry in 2,3-Anhydro-<i>O</i>-furanosides
  作者：Christopher S. Callam、Rajendrakumar Reddy Gadikota、Todd L. Lowary

  DOI：10.1021/jo001747a

  日期：2001.6.1

  3-anhydro-S-glycosides, the size of the (1)J[C(1)-H(1)] is not sensitive to C(1) stereochemistry. Computational studies on all four methyl 2,3-anhydro-O-furanosides (5-8) demonstrated that (1)J[C(1)-H(1)] was inversely proportional to the length of the C(1)-H(1) bond. A previously reported equation, which relates C(1)-H(1) bond distance and atomic charges to (1)J[C(1)-H(1)] magnitudes, could be used to accurately

  在C，（1）和H（1）之间的2，3-脱水-O-呋喃糖苷之间的单键耦合常数的大小已显示对异头中心的立体化学敏感。研究了一组由24种化合物组成的化合物，如果将异头氢反式转化为环氧化物部分，则（1）J [C（1）-H（1）] = 163-168 Hz；而当氢为环氧乙烷环的顺式时，（（（1）J [C（1）-H（1）] = 171-174 Hz）。相反，对于2,3-脱水-S-糖苷， （1）J [C（1）-H（1）]对C（1）立体化学不敏感。对所有四种甲基2,3-脱水-O-呋喃糖苷（5-8）的计算研究表明（1 ）J [C（1）-H（1）]与C（1）-H（1）键的长度成反比。以前报道的方程式涉及C（1）-H（1）的键距和原子电荷到（1）J [C（1）-H（1）]量级，可用于准确预测α-lyxo（5）和beta-ribo（8）异构体的J值。相反，对于β-lyxo（6）和α-ribo异构体（7），该方程式将这些耦合常数的大小低估了10-20