methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside | 91852-14-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside
• 英文别名: methyl 2-azido-2-deoxy-4-O-(β-D-galactopyranosyl)-β-D-glucopyranoside；(2S,3R,4S,5R,6R)-2-[(2R,3S,4R,5R,6R)-5-azido-4-hydroxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 91852-14-1
• 化学式: C₁₃H₂₃N₃O₁₀
• 分子量: 381.34
• InChiKey: CSISODFNULUXOX-AQKZVIMPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.6
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  173
• 氢给体数：
  6
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 反应 4.0h， 生成 (2S,3R,4S,5S,6S)-2-((2R,3S,4R,5R,6S)-5-Amino-4-hydroxy-2-hydroxymethyl-6-methoxy-tetrahydro-pyran-3-yloxy)-6-hydroxymethyl-tetrahydro-pyran-3,4,5-triol
  参考文献：
  名称：

  Wong, Ting C.; Lemieux, Raymond U., Canadian Journal of Chemistry, 1984, vol. 62, p. 1207 - 1213

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl O-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-(1<*>4)-3,6-di-O-acetyl-2-azido-2-deoxy-β-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以96%的产率得到methyl O-β-D-galactopyranosyl-(1-4)-2-azido-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Wong, Ting C.; Lemieux, Raymond U., Canadian Journal of Chemistry, 1984, vol. 62, p. 1207 - 1213

  摘要：

  DOI：

文献信息

• Lewissäure-katalysierte synthesen von di- und trisaccharid-sequenzen der O- und N-glycoproteine. Anwendung von trimethylsilyltrifluoromethanesulfonat
  作者：Hans Paulsen、Michael Paal

  DOI：10.1016/0008-6215(84)85005-3

  日期：1984.12

  Abstract In the presence of trimethylsilyltrifluoromethanesulfonate as Lewis acid catalyst, β-acetates reacted, as glycosyl donors and with neighboring-group participation, with secondary hydroxyl groups of saccharides having low reactivity to give β-glycosidically linked di- and oligo-saccharides in high yields. The protecting groups of both compounds of the reaction had to be stable under acid conditions

  摘要在三甲基甲硅烷基三氟甲磺酸酯作为路易斯酸催化剂的存在下，β-乙酸酯作为糖基供体并与邻近基团反应，与低反应性的糖的仲羟基反应，从而以高收率得到β-糖苷键合的二糖和寡糖。该反应的两种化合物的保护基必须在酸性条件下是稳定的。因此，1,2,3,4,6-戊基-O-乙酰基-β-d-吡喃半乳糖与甲基2-叠氮基-4,6-二-O-苯甲酰基-2-脱氧-β-d-的反应半乳糖吡喃糖苷以83％的收率得到甲基2-叠氮基-2,6-二-O-苯甲酰基-2-脱氧-3-O-（2,3,4,6-四-O-乙酰基-β-d- （吡喃半乳糖）-β-d-吡喃半乳糖苷是有用的构建单元。比较了路易斯酸催化和Koenigs-Knorr条件下的糖苷反应。
• Syntheses of Modified Carbohydrates with Glycosidases: Stereo- and Regiospecific Syntheses of Lactosamine Derivatives and Related Compounds¹
  作者：Kurt G.I. Nilsson、Hefeng Pan、Ulla Larsson-Lorek

  DOI：10.1080/07328309708007328

  日期：1997.5

  Abstract Different lactosamine derivatives, modified in the 2-N- and anomeric positions and suitable as intermediates for synthesis of Lewis-x and related compounds, were prepared with high specificity on a multigram scale directly from lactose, employing different D-glucosamine derivatives as acceptors and the abundant β-D-galactosidase from Bullera singularis as catalyst. Thus, methyl O-β-D-gala

  摘要以不同的D-葡萄糖胺衍生物为接受剂，直接从乳糖以高克数级制备了在2-N-和端基异构体位置修饰，适合作为Lewis-x及相关化合物合成中间体的不同乳糖胺衍生物。并以奇异布拉氏菌中丰富的β-D-半乳糖苷酶为催化剂。因此，甲基O-β-D-吡喃半乳糖基-（1→4）-2-叠氮基-2-脱氧-β-D-吡喃葡萄糖苷，乙基O-β-D-吡喃半乳糖基-（1→4）-2-脱氧- 2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃葡萄糖苷和乙基O-β-D-吡喃半乳糖基-（1→4）-2-脱氧-2-（2,2,2-三氯乙氧基羰基氨基）-1-硫基-β -D-吡喃葡萄糖苷以基于添加的受体计算的20-40％的产率形成。不经色谱法（萃取/结晶步骤）分离出结晶形式的2-邻苯二甲酰亚胺基衍生物。三糖衍生物乙基O-β-D-吡喃半乳糖-（1→4）-O-β-D-吡喃半乳糖-（1→4）-2-脱氧-2-邻苯二甲酰亚胺基-1-硫代-β-D-吡喃葡萄糖苷也孤立。对应
• Synthesis of Lewis X and three Lewis X trisaccharide analogues in which glucose and rhamnose replace N-acetylglucosamine and fucose, respectively
  作者：Ari Asnani、France-Isabelle Auzanneau

  DOI：10.1016/j.carres.2008.04.017

  日期：2008.7

  Three analogues of the Le(x) trisaccharide: alpha-L-Fucp-(1 -> 3)-[beta-D-Galp-(1 -> 4)]-D-GlcNAcp as well as the Le(x) trisaccharide itself were synthesized as methyl glycosides. In the analogues, either only the fucose residue is replaced by rhamnose or both the N-acetylglucosamine and the fucosyl residues are replaced by glucose and rhamnose, respectively. Our synthetic strategy relied on the use of lactoside and 2-azido lactoside derivatives as disaccharide acceptors, which were submitted to either fucosylation or rhamnosylation. Our results confirm that the reactivity of lactose in protection and glycosylation reactions is greatly affected by (1) the structure of the aglycone and (2) the presence of an azido substituent at C-2 of the glucose moiety. Thus, a methyl lactoside acceptor was easily glycosylated at O-3 with perbenzylated P-thiophenyl fucoside and rhamnoside to give anomerically pure alpha-fucosylated and alpha-rhamnosylated trisaccharides, respectively. In contrast, the same reactions on a 2-azido methyl lactoside acceptor led to the formation of anomeric mixtures. While the alpha- and beta-fucosylated 2-azido trisaccharides could be separated by RP-HPLC, such separation was not possible for the rharmnosylated anomers. The desired rhamnosylated trisaccharide was finally obtained anomerically pure using an isopropylidene-protected rhanmosyl donor. The deprotection sequences also showed that the presence of a 2-azido substituent at C-2 of the glucose residue conferred stability to the vicinal facosidic linkage at C-3. To test their relative affinity for anti-Le(x) Abs the Lex analogues will be used as competitive inhibitors against methyl Le(x). In addition, their conformational behavior will be studied by NMR spectroscopy and molecular modeling experiments. (C) 2008 Elsevier Ltd. All rights reserved.
• Selective Protection of 2-Azido-lactose and in Situ Ferrier Rearrangement during Glycosylation:  Synthesis of a Dimeric Lewis X Fragment
  作者：An Wang、France-Isabelle Auzanneau

  DOI：10.1021/jo062541y

  日期：2007.4.1

  In our efforts to design new anti-cancer vaccines based on the tumor associated carbohydrate antigen dimeric Le(x), we have synthesized the fragment GlcNAc-beta-(1 -> 3)-Gal-beta-(1 -> 4)-GlcNAc-beta-(1 -> O)-Me. Although it is notoriously difficult to chemically protect the primary OH groups in beta-lactoside derivatives, a 6,6'-disilylated intermediate was prepared in 82% yield. It was converted to a glycosyl acceptor free at O-3' that was glycosylated with a 2-deoxy-2-phthalimido trichloroacetimidate glucosyl donor. This glycosylation required large amounts of TMSOTf to proceed. Such conditions led to the formation of a Ferrier rearrangement glycosylation product. Despite these hurdles, the desired trisaccharide was isolated in 53% yield and easily deprotected in four steps.