methyl 2,4-di-O-benzoyl-α-L-rhamnopyranoside | 88331-96-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,4-di-O-benzoyl-α-L-rhamnopyranoside
• 英文别名: [(2S,3R,4R,5R,6R)-5-benzoyloxy-4-hydroxy-6-methoxy-2-methyloxan-3-yl] benzoate
• CAS: 88331-96-8
• 化学式: C₂₁H₂₂O₇
• 分子量: 386.401
• InChiKey: JIUIYTBSGPDHPY-HUSRDKOHSA-N

物化性质

• 沸点：
  562.5±50.0 °C(predicted)
• 密度：
  1.30±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

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 2,4-di-O-benzoyl-α-L-rhamnopyranoside 在 palladium on activated charcoal 2,4,6-三甲基吡啶 、 1,1-二氯甲醚 、 氢气 、 sodium methylate 、 silver trifluoromethanesulfonate 、 zinc(II) chloride 作用下， 以 二氯甲烷 、 氯仿 、 乙二醇甲醚 、 水 、 甲苯 为溶剂， 反应 22.33h， 生成 Methyl O-α-L-rhamnopyranosyl-(1->3)-O-α-L-rhamnopyranosyl-(1->2)-α-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of ligands related to the O-specific antigen of type 1 Shigella dysenteriae. 3. Glycosylation of 4,6-O-substituted derivatives of methyl 2-acetamido-2-deoxy-.alpha.-D-glucopyranoside with glycosyl donors derived from mono- and oligosaccharides.

  摘要：

  Methyl O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside, obtained by silver trifluoromethanesulfonate-mediated condensation of methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside and 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl bromide (3), was cleaved with dichloromethyl methyl ether (DCMME) to give O-(2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl)-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl chloride (9). Condensations of 1,3,4,6-tetra-O-acetyl-alpha-D-galactopyranose with 3 and 9, followed by treatment of the products with DCMME yielded, respectively, glycosyl chlorides 12 and 17. Each of these, as well as 2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl chloride was condensed with 4,6-O-substituted (benzylidene, tetraisopropyl-disiloxane-1,3-diyl, or benzyl) derivatives of methyl 2-acetamido-2-deoxy-alpha-D-glucopyranoside, using CH2Cl2, ether, or a mixture thereof as the solvent. The formation of the desired alpha-D-galactopyranosyl linkage was favored when ether was the solvent. Under these conditions, however, the combined yield of the condensation products decreased, especially when less reactive synthons were used. The alpha-linked products obtained were deprotected to give the methyl alpha-glycosides of the tetra, tri-, and the disaccharide related to the chemical repeating unit of the O-specific side chain of the lipopolysaccharide of Shigella dysenteriae type 1. Synthesis of methyl alpha-glycosides of three other constituents of the same polymeric antigen [alpha-L-Rha-(1 --> 3)-alpha-L-Rha, alpha-L-Rha-(1 --> 2)-alpha-D-Gal, and alpha-L-Rha-(1 --> 3)-alpha-L-Rha-(1 --> 2)-alpha-D-Gal] are also described.

  DOI：

  10.1021/jo00034a047
• 作为产物：
  描述：

  甲基 2,3-O-异亚丙基-alpha-L-吡喃鼠李糖苷 在 吡啶 、 D(+)-10-樟脑磺酸 、 三氟乙酸 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 3.72h， 生成 methyl 2,4-di-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  痢疾志贺氏菌1型O特异性多糖的八糖片段的融合合成。

  摘要：

  描述了线性八糖甲基糖苷α-L-Rhap-（1-> 2）-alpha-D-Gal p-（1> 3）-alpha-Glc p NAc-（ 1-> 3）-al pha-L-Rha p-（1-> 3）-alpha-L-Rha p-（1-> 2）-alpha-D-Gal p-（1-> 3）-α-D-Glcp NAc-（1→3）-α-L-Rhap-OMe（11），其对应于痢疾志贺氏菌1型的O特异性多糖的两个连续重复单元。

  DOI：

  10.1016/0008-6215(94)84079-2

文献信息

• Phenylselenoglycosides as novel, versatile glycosyl donors. Selective activation over thioglycosides
  作者：Seema Mehta、B. Mario Pinto

  DOI：10.1016/0040-4039(91)80005-q

  日期：1991.1

  of phenylselonoglycosides over ethylthioglycosides with silver trifluoromethanesulfonate and anhydrous potassium carbonate gives an efficient synthesis of disaccharides from selenoglycoside donors and thioglycoside acceptors. Activation is quenched by addition of 1,1,3,3,-tetramethylurea or collidine.

  用三氟甲磺酸银和无水碳酸钾对乙基巯基糖苷在乙基硫代糖苷上的选择性活化，可以从硒代糖苷供体和硫代糖苷受体高效合成二糖。通过添加1,1,3,3，-四甲基脲或可力丁淬灭活化。
• Synthèses du β-<scp>L</scp>-rhamnopyranoside d'hordénine et d'acylgluco-<scp>L</scp>-rhamnopyranoses peracétylés
  作者：Nadia Boughandjioua、Lin Rui Chao、Alexios-Leandros Skaltsounis、Elisabeth Seguin、François Tillequin、Michel Koch

  DOI：10.1139/v92-245

  日期：1992.7.1

  The stereoselective synthesis of hordenine β-L-rhamnopyranoside (3) was achieved using 4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide (14) as key intermediate. The regiospecific syntheses of the peracetyl derivatives of (E)-O-(6-O-cinnamoyl-β-D-glucopyranosyl)-(1 → 2)-, (1 → 3)-, and (1 → 4)-α-L-rhamnopyranoses and of their 4-acetoxycinnamoyl counterparts were achieved through the use of various types of rhamnose-derived intermediates, i.e., 1,2-O-orthoester for the (1 → 2) series, 2,3-O-orthoester for the (1 → 3) series, and 2,3-O-isopropylidene for the (1 → 4) series.

  使用4-O-乙酰基-2,3-O-羰基-α-L-鼠李糖基溴化物（14）作为关键中间体，实现了异构选择性合成鼠李糖基β-L-喝荡碱苷（3）。通过使用不同类型的鼠李糖衍生中间体，即1,2-O-正交酯用于（1→2）系列，2,3-O-正交酯用于（1→3）系列，以及2,3-O-异丙基亚甲基用于（1→4）系列，实现了（E）-O-(6-O-肉桂酰基-β-D-葡萄糖基)-(1→2)-、(1→3)-和(1→4)-α-L-鼠李糖苷的特定区域合成以及它们的4-乙酰氧基肉桂酰基对应物的合成。
• Articial carbohydrate antigens: A block synthesis of a linear, tetrasaccharide repeating-unit of the Shigella flexneri varianty polysaccharide
  作者：Hans-Peter Wessel、David R. Bundle

  DOI：10.1016/0008-6215(83)88465-1

  日期：1983.12

  beta-D-glucopyranosyl-(1----2)-alpha-L- rhamnopyranoside. Together with previously synthesized tetrasaccharides of the Shigella flexneri Y O-antigen, this oligosaccharide has been used to study the conformation of O-antigens and to assist in the selection of S. flexneri, variant Y, specific monoclonal antibodies.

  甲基2,4-二-O-苯甲酰基-α-L-鼠李吡喃糖苷与2,3,4-三-O-乙酰基-α-L-鼠李糖吡喃糖苷的糖基化反应得到甲基2,4-二-O-苯甲酰基-3 -O-（2,3,4-三-O-乙酰基-α-L-鼠李吡喃糖基）-α-L-鼠李糖吡喃糖苷（4），产率为93％。用二溴甲基甲基醚将4转化成相应的糖基溴化物。在Koenigs-Knorr条件下，该溴化物与8-（甲氧羰基）辛基2-O-（2-乙酰氨基-4,6-O-亚苄基-2-脱氧-β-D-甘露糖基）-3,4-二-反应O-苄基-α-L-鼠李吡喃糖苷，以91％的产率提供被保护的四糖。去除保护基团得到8-（甲氧基羰基）辛基O-α-L-鼠李吡喃糖基-（1 ---- 3）-O-α-L-鼠李吡喃糖基-（1 ---- 3）-O-2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖基-（1 ---- 2）-α-L-鼠李糖吡喃糖苷。
• A general method for the synthesis of oligosaccharides consisting of α-(1→2)- and α-(1→3)-linked rhamnan backbones and GlcNAc side chains
  作者：Jianjun Zhang、Fanzuo Kong

  DOI：10.1016/s0040-4020(03)00075-9

  日期：2003.2

  and 3-O-acetyl-2,4-di-O-benzoyl-α-l-rhamnopyranosyl trichloroacetimidate, which were obtained by highly regioselective 3-O-acylations, were used as the key synthons to obtain the required α-(1→2)- and α-(1→3)-linked rhamnoocta saccharide acceptors with 33- and 37-free hydroxyl groups. Therefore, several disaccharides were synthesized, from which tetrasaccharides and hexasaccharides were then synthesized

  已经开发了用于合成由具有GlcNAc侧链的（1→2）-和（1→3）-连接的鼠李糖寡糖组成的寡糖的一般方法。例如，在植物致病性细菌丁香假单胞菌pv的脂多糖的O多糖部分中的两个十糖的高效且收敛的合成。获得了ribicola NCPPB 1010。这两个十糖分别由O多糖重复单元I + II和II + I组成。烯丙基3- ø -乙酰基-4- ö苯甲酰基α-L-吡喃鼠李糖苷，烯丙基2- ø -苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖苷，2,4-二- ö苯甲酰基-3- ø -氯乙酰-α-L-吡喃鼠李糖三氯乙酰亚胺酯，和3- ö -乙酰基-2,4-二- ö苯甲酰基α-L-吡喃鼠李糖三氯乙酰亚胺酯，这是由高度选择性3-O-获得酰化用作关键合成子，以得到所需的具有3 3-和3 7-游离羟基的α-（1→2）-和α-（1→3）连接的鼠李糖单糖受体。因此，合成了几种二糖，然后由它们合成了四糖和六糖。六糖供
• Synthesis of tri- and tetrasaccharide fragments of the Shigella dysenteriae type 1 O-antigen deoxygenated and fluorinated at position 3 of the methyl α-d-galactopyranoside terminus1Part 10 of the series Synthesis of ligands related to the O-specific antigen of Shigella dysenteriae type 1. For part 9 see ref[1].1
  作者：Laurence A. Mulard、Cornelis P.J. Glaudemans

  DOI：10.1016/s0008-6215(98)00216-x

  日期：1998.9

  The blockwise synthesis of methyl alpha tri- and tetrasaccharide analogs of the biochemical repeating unit of the Shigella dysenteriae type 1 O-polysaccharide is described. Modifications include deoxygenation and deoxyfluorination at position 3 of the galactopyranoside residue. Methyl 4,6-O-benzylidene-3-deoxy-alpha-D-xylo-hexopyranoside (8) and methyl 4,6-O-benzylidene-3-deoxy-3-fluoro-alpha-D-galactopyranoside

  描述了痢疾志贺氏菌1O型多糖的生化重复单元的甲基α三和四糖类似物的嵌段合成。修饰包括在吡喃半乳糖苷残基的3位上的脱氧和脱氧氟化。分别是甲基4,6-O-亚苄基-3-脱氧-α-D-木基己吡喃糖苷（8）和甲基4,6-O-亚苄基-3-脱氧-3-氟-α-D-吡喃半乳糖苷（9）。与（2,3,4-三-O-苯甲酰基-α-L-鼠李糖基吡喃糖基）-（1-> 3）-2,4-二-O-苯甲酰基-α-L-鼠李糖基氯缩合得到脱保护，目标三糖甲基α-L-鼠李吡喃糖基-（1-> 3）-α-L-鼠李糖吡喃糖基-（1-> 2）-3-脱氧-α-D-木糖己吡喃糖苷和相应的氟化寡糖。对于四糖合成，糖基受体8和9与暂时保护的（2,4-二-O-苯甲酰基-3-O-氯乙酰基-α-L-鼠李糖基吡喃糖基）-（1→3）-2,4-二- O-苯甲酰基-α-L-鼠李糖基氯。除去氯乙酰基后，将所得的选择性解封闭的三糖与3,4,6-三-O-乙酰基-2-叠氮