4-methoxybenzyl 2,4-di-O-benzyl-α-L-rhamnopyranoside | 128716-44-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-methoxybenzyl 2,4-di-O-benzyl-α-L-rhamnopyranoside
• 英文别名: (2R,3R,4R,5R,6S)-2-[(4-methoxyphenyl)methoxy]-6-methyl-3,5-bis(phenylmethoxy)oxan-4-ol
• CAS: 128716-44-9
• 化学式: C₂₈H₃₂O₆
• 分子量: 464.558
• InChiKey: CSXUEKJZXQJZQC-YKKLQROBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  34
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-methoxybenzyl 2,4-di-O-benzyl-α-L-rhamnopyranoside 在 硼烷四氢呋喃络合物 、 sodium methylate 、 silver carbonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 8.5h， 生成 4-methoxybenzyl 2,4-di-O-benzyl-3-O-(2-acetamido-2-deoxy-β-D-mannopyranosyl)-α-L-rhamnopyranoside
  参考文献：
  名称：

  Syntheses of Three Interglycosidic Isomers of N-Acetyl-.BETA.-D-mannosaminyl-L-rhamnoses Associated with O-Antigens of Several Gram-Negative Opportunistic Pathogens.

  摘要：

  我们实现了N-乙酰基-β-D-甘露糖胺酰-L-鼠李糖三种糖苷间异构体的实用、高度立体选择性合成，其中β(1→4)异构体对应于机会性病原体铜绿假单胞菌O5和铜绿假单胞菌X（Meitert）的脂多糖（LPS）O抗原的重复单元。其他异构体是β(1→2)二糖（大肠杆菌O1A的LPS的成分）和人工β(1→3)异构体。二糖是通过简单的三步反应序列从2-(苯甲酰氧亚氨基)-2-脱氧糖基卤化物（甘露糖胺前体）获得的。对适当保护的L-鼠李糖基受体进行了β选择性糖基化。随后将2-酰氧亚氨基官能团还原为氨基，进行N-乙酰化，并去除保护基团，从而得到目标二糖。13C-NMR和核Overhauser效应谱被证明可用于确定二糖位置异构体的结构。

  DOI：

  10.1248/cpb.43.1441
• 作为产物：
  描述：

  4-methoxybenzyl 4-O-benzyl-α-L-rhamnopyranoside 、 溴甲苯 在 四丁基溴化铵 sodium hydroxide 作用下， 以 二氯甲烷 为溶剂， 以91%的产率得到4-methoxybenzyl 2,4-di-O-benzyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  合成的6A和6B型肺炎链球菌荚膜多糖的选择性保护的三糖结构单元。

  摘要：

  4-甲氧基苄基2,4-二-O-苄基-3-O- [2,4,6-三-O-苄基-3-O-（3,4,6-三-O-苄基-α-D -半乳糖吡喃糖基）-α-D-吡喃葡萄糖基]-α-L-鼠李糖吡喃糖苷（22），α-D-Galp-（1 ---- 3）-alpha-D-Glcp-（1- --3）肺炎链球菌6A和6B型荚膜多糖的α-L-Rhap片段[---- 2）-α-D-Galp-（1 ---- 3）-α-D-Glcp -（1 ---- 3）-alpha-L-Rhap-（1 ---- X）-D- RibOH-（5-P ----] n（6A，X = 3; 6B，X = 4）已经合成了乙基3-O-烯丙基-2,4,6-三-O-苄基-1-硫代-β-D-吡喃葡萄糖苷与4-甲氧基苄基2,4-二-O-苄基-以三氟甲磺酸甲酯为促进剂，在乙醚中形成α-L-鼠李糖吡喃糖苷，将所得的α-D-Glcp-（1 ---- 3）-α-L-

  DOI：

  10.1016/0008-6215(89)85090-6

文献信息

• An Alternative Access to a Trisaccharide Repeating Unit of the Capsular Polysaccharide of Streptococcus pneumoniae Serotype 19A.
  作者：Eisuke KAJI、Yumiko OSA、Mutsumi TANAIKE、Yugo HOSOKAWA、Hiroaki TAKAYANAGI、Atsushi TAKADA

  DOI：10.1248/cpb.44.437

  日期：——

  A chemical synthesis has been achieved for beta-D-ManNAc-(1-->4)-alpha-D-Glc-(1-->3)-L-Rha, a trisaccharide repeating unit of the capsular polysaccharide of Streptococcus pneumoniae serotype 19A, by stepwise link-up of the suitably functionalized, constituent sugar units. A beta-selective glycosylation of trimethylsilylethyl glucoside having free 4-OH with 2-(benzoyloxyimino)-2-deoxyglycosyl bromide

  化学合成已经实现了β-D-ManNAc-（1→4）-α-D-Glc-（1→3）-L-Rha，这是肺炎链球菌荚膜多糖的三糖重复单元。通过逐步连接适当官能化的糖单元，获得血清型19A。用2-（苯甲酰氧基亚氨基）-2-脱氧糖基溴化物将具有游离4-OH的三甲基甲硅烷基乙基葡糖苷进行β选择性糖基化，然后进行甘露聚糖选择性硼氢化，N-乙酰化和异头中心官能化（1-OSE-> 1 -OH-> 1-F），得到关键的二糖供体，β-D-ManNAc-（1-> 4）-alpha-D-Glc-（1-> F.L-鼠李糖基糖基化解封后，具有供体底物的受体受体在13步中从D-葡萄糖以6.5％的产率提供了目标三糖。
• A new route for the synthesis of Streptococcus pneumoniae 19F and 19A capsular polysaccharide fragments avoiding the β-mannosamine glycosylation step
  作者：Filippo Bonaccorsi、Giorgio Catelani、Stefan Oscarson

  DOI：10.1016/j.carres.2009.04.012

  日期：2009.8

  The recently described [Attolino, E.; Bonaccorsi, F.: Catelani, G.; D'Andrea, F. Carbohydr. Res. 2008, 343, 2545-2556.] beta-D-MaNAcp-(1 -> 4)-beta-D-Glcp thiophenyl glycosyl donor 3 was used in alpha-glycosylation reactions of OH-2 and OH-3 of the suitably protected p-MeO-benzyl alpha-L-rhamnopyranoside acceptors 7 and 8. Glycosylation of the axial OH-2 of 7 took place in high yield (76%) and with acceptable stereoselectivity (alpha/beta = 3.4) leading to the protected trisaccharide alpha-11, corresponding to the repeating unit of Streptococcus pneumoniae 19F. The same reaction on equatorial OH-3 of acceptor 8 gave the trisaccharide alpha-15, a constituent of the repeating unit of S. pneumoniae 19A, but in lower yield (41%) and without stereoselection (alpha/beta = 1:1.3). Utilizing the introduced orthogonal protection of OH-1 and OH-4 '', the trisaccharide alpha-11 was transformed into a trisaccharide building block suitable for the synthesis of its phosphorylated oligomers. (C) 2009 Elsevier Ltd. All rights reserved.
• SLAGHEK, TED M.;VAN, VLIET MICHIEL J.;MAAS, AUGUSTINUS A. M.;KAMERLING, J+, CARBOHYDR. RES., 195,(1989) N, C. 75-86
  作者：SLAGHEK, TED M.、VAN, VLIET MICHIEL J.、MAAS, AUGUSTINUS A. M.、KAMERLING, J+

  DOI：——

  日期：——
• Synthesis of a selectively protected trisaccharide building block of the capsular polysaccharide of streptococcus pneumoniae types 6A and 6B
  作者：Ted M. Slaghek、Michiel J. van Vliet、Augustinus A.M. Maas、Johannis P. Kamerling、Johannes F.G. Vliegenthart

  DOI：10.1016/0008-6215(89)85090-6

  日期：1989.12

  amnopyranoside (22), a building block for the alpha-D-Galp-(1----3)-alpha-D-Glcp-(1----3)-alpha-L-Rhap fragment of the capsular polysaccharides of Streptococcus pneumoniae types 6A and 6B [----2)-alpha-D-Galp-(1----3)-alpha-D-Glcp-(1----3)-alpha-L-Rhap-( 1----X)-D- RibOH-(5-P----]n (6A, X = 3; 6B, X = 4) has been synthesised. Ethyl 3-O-allyl-2,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside was coupled

  4-甲氧基苄基2,4-二-O-苄基-3-O- [2,4,6-三-O-苄基-3-O-（3,4,6-三-O-苄基-α-D -半乳糖吡喃糖基）-α-D-吡喃葡萄糖基]-α-L-鼠李糖吡喃糖苷（22），α-D-Galp-（1 ---- 3）-alpha-D-Glcp-（1- --3）肺炎链球菌6A和6B型荚膜多糖的α-L-Rhap片段[---- 2）-α-D-Galp-（1 ---- 3）-α-D-Glcp -（1 ---- 3）-alpha-L-Rhap-（1 ---- X）-D- RibOH-（5-P ----] n（6A，X = 3; 6B，X = 4）已经合成了乙基3-O-烯丙基-2,4,6-三-O-苄基-1-硫代-β-D-吡喃葡萄糖苷与4-甲氧基苄基2,4-二-O-苄基-以三氟甲磺酸甲酯为促进剂，在乙醚中形成α-L-鼠李糖吡喃糖苷，将所得的α-D-Glcp-（1 ---- 3）-α-L-
• Syntheses of Three Interglycosidic Isomers of N-Acetyl-.BETA.-D-mannosaminyl-L-rhamnoses Associated with O-Antigens of Several Gram-Negative Opportunistic Pathogens.
  作者：Eisuke KAJI、Noriko ANABUKI、Shonosuke ZEN

  DOI：10.1248/cpb.43.1441

  日期：——

  We achieved practical, highly stereoselective syntheses of three interglycosidic isomers of N-acetyl-β-D-mannosaminyl-L-rhamnoses, among which a β(1→4)-isomer corresponds to the repeating unit of the O-antigen of lipopolysaccharide (LPS) from the opportunistic pathogens Pseudomonas cepacia O5 and Pseudomonas aeruginosa X (Meitert). The other isomers are a β(1→2)-disaccharide, a constituent of LPS from Escherichia coli O1A, and an artificial β(1→3)-isomer. The disaccharides were obtained by simple three-step reaction sequences from 2-(benzoyloxyimino)-2-deoxyglycosyl halides (mannosamine progenitor). β-Selective glycosylations of appropriately protected L-rhamnosyl acceptors were performed. Subsequent reduction of the 2-acyloxyimino function to an amino group, N-acetylation, and removal of the protecting groups provided the target disaccharides. 13C-NMR and nuclear Overhauser effect spectra proved to be useful for stractural determination of the positional isomers of the disaccharides.

  我们实现了N-乙酰基-β-D-甘露糖胺酰-L-鼠李糖三种糖苷间异构体的实用、高度立体选择性合成，其中β(1→4)异构体对应于机会性病原体铜绿假单胞菌O5和铜绿假单胞菌X（Meitert）的脂多糖（LPS）O抗原的重复单元。其他异构体是β(1→2)二糖（大肠杆菌O1A的LPS的成分）和人工β(1→3)异构体。二糖是通过简单的三步反应序列从2-(苯甲酰氧亚氨基)-2-脱氧糖基卤化物（甘露糖胺前体）获得的。对适当保护的L-鼠李糖基受体进行了β选择性糖基化。随后将2-酰氧亚氨基官能团还原为氨基，进行N-乙酰化，并去除保护基团，从而得到目标二糖。13C-NMR和核Overhauser效应谱被证明可用于确定二糖位置异构体的结构。