methyl 3,4-di-O-benzoyl α-L-rhamnopyranoside | 51288-33-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4-di-O-benzoyl α-L-rhamnopyranoside
• 英文别名: methyl 3,4-di-O-benzoyl-α-L-rhamnopyranoside；methyl-3,4-di-O-benzoyl-α-L-rhamnopyranoside；[(2S,3S,4S,5R,6R)-4-benzoyloxy-5-hydroxy-6-methoxy-2-methyloxan-3-yl] benzoate
• CAS: 51288-33-6；122805-37-2；135216-57-8；148081-33-8；89756-09-2
• 化学式: C₂₁H₂₂O₇
• 分子量: 386.401
• InChiKey: KNXFDCRHSIHWIP-JTIRBEDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 3,4-di-O-benzoyl α-L-rhamnopyranoside 在 偶氮二异丁腈 、 溴 、 三正丁基氢锡 、 N,N-二甲基苯胺 作用下， 以 苯 为溶剂， 反应 29.5h， 生成 methyl 3,4-di-O-benzoyl-β-L-rhamnopyranoside
  参考文献：
  名称：

  Chemistry of 1-Alkoxy-1-glycosyl Radicals:  The Manno- and Rhamnopyranosyl Series. Inversion of α- to β-Pyranosides and the Fragmentation of Anomeric Radicals

  摘要：

  The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.

  DOI：

  10.1021/jo951194h
• 作为产物：
  描述：

  methyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranoside 在 盐酸 作用下， 反应 16.0h， 以90%的产率得到methyl 3,4-di-O-benzoyl α-L-rhamnopyranoside
  参考文献：
  名称：

  Synthesis of the principal chain of the 0-antigenic polysaccharides ofShigella flexneri Communication 1. Synthesis of 2,4- and 3,4-di-o-benzoyl-?-L-rhamnopyranosides by a combination of selective acylation and deacetylation, and the synthesis of 1,2-di-o-acetyl-3,4-di-o-benzoyl-L-rhamnopyranose via 1,2-o-benzylidene-3,4-di-o-benzoyl-?-L-rhamnopyranose

  摘要：

  DOI：

  10.1007/bf01142795

文献信息

• Studies on the conformational flexibility of α-l-rhamnose-containing oligosaccharides using 13C-site-specific labeling, NMR spectroscopy and molecular simulations: implications for the three-dimensional structure of bacterial rhamnan polysaccharides
  作者：K. Hanna M. Jonsson、Elin Säwén、Göran Widmalm

  DOI：10.1039/c2ob06924e

  日期：——

  together with total line-shape analysis were used to extract conformationally dependent hetero- and homonuclear spin–spin coupling constants. This resulted in the determination of 2JC2′,H1′, 3JC1′,C1, 3JC1′,C3, 3JC2′,C2, 2JC1′,C2, 1JC1′,C2′, and 1JC1′,H1′. These data together with previously determined JCH and 1H,1H NOEs result in fourteen conformationally dependent NMR parameters that are available

  细菌多糖由多种单糖组成， 大号鼠李糖 （6-脱氧-L-甘露糖）成为其中的一员。这种糖经常是α-的一部分（1→2） -和/或α-（1→3） -键，所以我们研究了二糖α-大号-RHA p - （1→2）-α-大号- Rha p -OMe可在此糖苷键上获得构象偏好信息。目标二糖用合成13在C1'和C2在'C位点特异性标记，我。例如，在终端组中。2D 1 H，13 C-HSQC-HECADE和1 H，13 C-J-HMBC NMR实验，1D 13 C和11 H NMR光谱和总的线形分析用于提取构象相关的异核和同核自旋-自旋偶合常数。这导致的判断2 Ĵ C2'，H1' ，3 Ĵ C1'，C1，3 Ĵ C1'，C3，3 Ĵ C2'，C2，2 Ĵ C1'，C2，1 Ĵ C1'，C2' ，和1 J C1'，H1'。这些数据与先前确定的J CH和1 H，1H NOEs产生14个构象相关的NMR参数，可用于分析糖苷键的柔性和构象偏好。二糖的100
• TsOH-catalyzed acyl migration reaction of the Bz-group: innovative assembly of various building blocks for the synthesis of saccharides
  作者：Xing-Yong Liang、An-Lin Liu、Hua-Jun Shawn Fan、Lei Wang、Zhi-Ning Xu、Xin-Gang Ding、Bo-Shun Huang

  DOI：10.1039/d2ob02052a

  日期：——

  We developed an efficient method to achieve the regioselective acyl migration of benzoyl ester. In all the cases, the reactions required only the commercially available organic acid catalyst TsOH·H2O. This method enables the benzoyl group to migrate from secondary groups to primary hydroxyl groups, or from equatorial secondary hydroxyl groups to axial hydroxyl groups. The 1,2 or 1,3 acyl migration

  我们开发了一种有效的方法来实现苯甲酰酯的区域选择性酰基迁移。在所有情况下，反应只需要市售的有机酸催化剂 TsOH·H 2 O。该方法使苯甲酰基从仲羟基迁移到伯羟基，或从赤道仲羟基迁移到轴向羟基。1,2 或 1,3 酰基迁移可能通过五元和六元环邻位发生酸中间体。合成了范围广泛的正交保护单糖，它们是合成天然低聚糖的有用中间体。最后，为了证明该方法的实用性，组装了来自分枝杆菌细胞壁多糖的四糖部分。
• Synthesis of the O-specific polysaccharide of
  作者：N.K. Kochetkov、N.É. Byramova、Yu.E. Tsvetkov、L.V. Backinowsky

  DOI：10.1016/s0040-4020(01)96688-8

  日期：1985.1
• Synthesis of the principal chain of the o-antigenic polysaccharides ofShigella flexneri. Communication 4. Synthesis of 1,3-di-o-acetyl-4,6-di-o-benzoyl-2-desoxy-2-phthalimido-D-glucopyranose and 1-o-acetyl-2-o-(3-o-acetyl-4,6-di-o-benzoyl-2-desoxy-2-phthalimido-?-D-glucopyranosyl)-3,4-di-o-benzoyl-L-rhamnopyranose
  作者：N. �. Bairamova、L. V. Bakinovskii、N. K. Kochetkov

  DOI：10.1007/bf01142798

  日期：1985.5
• Selective removal of O-acetyl groups in the presence of O-benzoyl groups by acid-catalysed methanolysis
  作者：Narguiz É. Byramova、Michael V. Ovchinnikov、Leon V. Backinowsky、Nikolay K. Kochetkov

  DOI：10.1016/0008-6215(83)88370-0

  日期：1983.12