2,3,5-tri-O-benzoyl-D-arabinofuranosyl bromide | 56271-35-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,5-tri-O-benzoyl-D-arabinofuranosyl bromide
• 英文别名: [(2R,3R,4S)-3,4-dibenzoyloxy-5-bromooxolan-2-yl]methyl benzoate
• CAS: 56271-35-3
• 化学式: C₂₆H₂₁BrO₇
• 分子量: 525.353
• InChiKey: JRRCGOOKGUSEFK-SSWODZADSA-N

物化性质

• 沸点：
  611.4±55.0 °C(Predicted)
• 密度：
  1.49±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2,3,5-tri-O-benzoyl-D-arabinofuranosyl bromide 在 2,6-二甲基吡啶 、 gold(III) chloride 、 sodium methylate 、 四丁基碘化铵 、 sodium hydride 、 戴斯-马丁氧化剂 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 14.0h， 生成
  参考文献：
  名称：

  Gold(III)-Catalyzed Glycosidations for 1,2-trans and 1,2-cis Furanosides

  摘要：

  Stereoselective synthesis of furanosides is still a daunting task, unlike the pyranosides, for which several methods exist. Herein, a unified stereoselective strategy for the synthesis of 1,2-trans and 1,2-cis furanosides is revealed for seven out of eight possible isomers of pentoses. The identified protocol gives access to diastereoselective synthesis of α- and β-araf, ribf, lyxf, and α-xylf furanosides. 1,2-trans glycosides were synthesized by the use of propargyl 1,2-orthoesters under gold-catalyzed glycosidation conditions, and subsequently, they are converted into 1,2-cis glycosides through oxidation-reduction as the key functional group transformation. All the reactions are found to be fully diastereoselective, mild, and high yielding.

  DOI：

  10.1021/jo501052y
• 作为产物：
  描述：

  methyl tri-O-benzoyl-α-D-arabinofuranoside 在 氢溴酸 、 溶剂黄146 作用下， 反应 2.0h， 以91%的产率得到2,3,5-tri-O-benzoyl-D-arabinofuranosyl bromide
  参考文献：
  名称：

  Khare, Naveen K.; Reynolds, Robert C.; Maddry, Joseph A., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2008, vol. 47, # 11, p. 1748 - 1752

  摘要：

  DOI：

文献信息

• Ready Preparation of Furanosyl<i>n</i>-Pentenyl Orthoesters from Corresponding Methyl Furanosides
  作者：Changalvala V. S. Ramamurty、Parimala Ganney、C. Srinivas Rao、Bert Fraser-Reid

  DOI：10.1021/jo1021376

  日期：2011.4.1

  The 3,5-di-O-benzoyl n-pentenyl orthoesters of the four pentofuranoses have been prepared. The first key intermediate in each case is the methyl pentofuranoside(s), and a user-friendly procedure for the preparation of each, based on the Callam−Lowary precedent, is described, whereby formation of the crucial α/β anomeric mixture is optimized. The mixture is used directly to prepare the corresponding

  已经制备了四个戊呋喃糖酶的3，5-二-O-苯甲酰基正戊烯基原酸酯。在每种情况下，第一个关键中间体是甲基呋喃呋喃糖苷，并且根据Callam-Lowary的先例，描述了一种方便的制备方法，用于制备每种戊呋喃糖苷，从而优化了关键的α/β异头混合物的形成。将该混合物直接用于制备相应的过苯甲酰化的呋喃呋喃糖基溴化物，然后制备标题化合物。
• Chemistry of β-trimethylsilylethanol. II. A new method for protection of an anomeric center in pyranosides
  作者：Bruce H. Lipshutz、Joseph J. Pegram、Matthew C. Morey

  DOI：10.1016/s0040-4039(01)82992-0

  日期：1981.1

  Protection of the anomeric center in various carbohydrates as a β-trimethylsilylethyl glycoside is reported. The free sugar can be regenerated using LiBF4 in acetonitrile.

  据报道，作为β-三甲基甲硅烷基乙基糖苷，各种碳水化合物中的异头异构中心得到保护。可以使用乙腈中的LiBF 4再生游离糖。
• Diastereoselective Ni-Catalyzed Negishi Cross-Coupling Approach to Saturated, Fully Oxygenated <i>C</i>-Alkyl and <i>C</i>-Aryl Glycosides
  作者：Hegui Gong、Michel R. Gagné

  DOI：10.1021/ja8041564

  日期：2008.9.10

  A Ni-catalyzed Negishi cross-coupling approach to C-glycosides is described with an emphasis on C-aryl glycosides. The combination of NiCl2/PyBox in N,N'-dimethylimidazolidinone (DMI) enabled the synthesis of C-alkyl glycosides under mild reaction conditions. Moderate yields and beta-selectivities were obtained for C-glucosides, and good yields and high alpha-selectivities were the norm for C-mannosides

  介绍了一种 Ni 催化的 Negishi 交叉偶联方法来处理 C-糖苷，重点是 C-芳基糖苷。NiCl2/PyBox 在 N,N'-二甲基咪唑烷酮 (DMI) 中的组合能够在温和的反应条件下合成 C-烷基糖苷。C-葡萄糖苷获得了中等的产量和β-选择性，而良好的产量和高α-选择性是C-甘露糖苷的标准。对于 C-芳基糖苷，在 N,N-二甲基甲酰胺 (DMF) 中使用 Ni(COD)2/(t)Bu-Terpy 的反应通常具有高产率，并提供具有高 β-选择性（1:>10 α: beta) 和 C-甘露糖苷具有中等 alpha 选择性 (3:1 alpha:beta)；α-C-芳基糖苷可以通过 Ni(COD)2/PyBox 在 DMF (>20:1 alpha:beta) 中的组合获得。集体研究表明，C-糖苷的立体化学控制取决于底物和催化剂的组合。Negishi 协议显示出出色的官能团耐受性，正如其在天然产物沙甲素
• Synthesis of arabinofuranose branched galactofuran tetrasaccharides, constituents of mycobacterial arabinogalactan
  作者：Lucía Gandolfi-Donadío、Malena Santos、Rosa M. de Lederkremer、Carola Gallo-Rodriguez

  DOI：10.1039/c0ob00989j

  日期：——

  Mycolyl-arabinogalactan (mAG) complex is a major component of the cell wall of Mycobacterium tuberculosis, the causative agent of tuberculosis disease. Due to the essentiality of the cell wall for mycobacterium viability, knowledge of the biosynthesis of the arabinogalactan is crucial for the development of new therapeutic agents. In this context, we have synthesized two new branched arabinogalactafuranose tetrasaccharides, decenyl β-D-Galf-(1→5)-β-D-Galf-(1→6)[α-D-Araf(1→5)]-β-D-Galf (1) and decenyl β-D-Galf-(1→6)-[α-D-Araf-(1→5)]-β-D-Galf-(1→5)-β-D-Galf (2), as interesting tools for arabinofuranosyl transferase studies. The aldonolactone strategy for the introduction of the internal D-Galf was employed, allowing the construction of oligosaccharides from the non-reducing to the reducing end. Moreover, a one-pot procedure was developed for the synthesis of trisaccharide lactone 21, precursor of 2, which involved a glycosylation-deprotection-glycosylation sequence, through the use of TMSOTf as catalyst of the trichloroacetimidate method as well as promoter of TBDMS deprotection.

  麦角糖阿拉伯半乳糖（mAG）复合物是结核分枝杆菌（Mycobacterium tuberculosis）细胞壁的重要组成部分，该菌是结核病的致病因子。由于细胞壁对分枝杆菌的生存至关重要，因此了解阿拉伯半乳糖的生物合成对于开发新的治疗药物具有重要意义。在此背景下，我们合成了两种新的分支型阿拉伯半乳糖呋喃糖四糖，分别为十烯基 β-D-Galf-(1→5)-β-D-Galf-(1→6)[α-D-Araf(1→5)]-β-D-Galf (1) 和十烯基 β-D-Galf-(1→6)-[α-D-Araf-(1→5)]-β-D-Galf-(1→5)-β-D-Galf (2)，作为阿拉伯呋喃糖基转移酶研究的有趣工具。采用了醇内酯策略引入内源性 D-Galf，使得可以从非还原端到还原端构建寡糖。此外，还开发了一种一锅法合成三糖内酯 21，它是 2 的前体，该方法涉及到糖苷化-去保护-糖苷化序列，采用 TMSOTf 作为三氯乙酰胺法的催化剂，以及 TBDMS 去保护的促进剂。
• Efficient synthesis of oligosaccharyl 1,2-O-orthoesters from n-pentenyl glycosides and application to the pentaarabinofuranoside of the mycobacterial cell surface
  作者：Shivaji A. Thadke、Srinivas Hotha

  DOI：10.1039/c4ob01395f

  日期：——

  Complex oligosaccharide syntheses employ the use of more than one glycosyl donor and hence, methods for the interconversion of glycosyl donors are highly valuable for the overall synthesis plan. Herein, n-pentenyl glycosides are efficiently converted to glycosyl 1,2-O-orthoesters in the presence of both acid and base sensitive functional groups. The identified protocol was found to be suitable for the synthesis of trisaccharyl and tetrasaccharyl 1,2-O-orthoester as well. Furthermore, an iterative synthesis of pentaarabinofuranoside present on the Mycobacterium tuberculosis cell surface was accomplished using this method.

  复杂的寡糖合成需要使用一个以上的糖基供体，因此，糖基供体之间的相互转化方法对整个合成计划非常重要。在这里，正戊烯基糖苷在酸和碱敏感官能团的存在下被有效地转化为糖基 1,2-O-正酯。发现所确定的方案也适用于合成三糖基和四糖基 1,2-O-缩酮。此外，该方法还完成了结核分枝杆菌细胞表面五碳呋喃糖苷的迭代合成。