methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside | 52885-40-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside
• 英文别名: (4aR,6R,7R,8R,8aR)-7-azido-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-8-ol
• CAS: 52885-40-2
• 化学式: C₁₄H₁₇N₃O₅
• 分子量: 307.306
• InChiKey: WCSBCLMCXJSBOJ-QFIBJEGBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside 在 palladium on activated charcoal 盐酸 、 sodium hydroxide 、 4 A molecular sieve 、 Dowex 50-X₈-200 (Na+ form) 、 氢气 、 silver trifluoromethanesulfonate 、 三甲基铵三氧化硫共聚物 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 80.0h， 生成 Sodium; (2S,3S,4S,5R,6R)-6-((2R,3R,4R,5R,6R)-3-amino-6-hydroxymethyl-2-methoxy-5-sulfooxy-tetrahydro-pyran-4-yloxy)-3,4,5-trihydroxy-tetrahydro-pyran-2-carboxylate
  参考文献：
  名称：

  硫酸皮肤素二糖片段的合成。

  摘要：

  结晶的2-叠氮基-4,6-O-亚苄基-2-脱氧-β-D-吡喃半乳糖酸甲酯与（2,3,4-三-O-乙酰基-α-L-氨基吡喃基溴化）尿酸甲酯在二氯甲烷中的缩合在三氟甲磺酸银和分子筛的存在下，提供了54％的甲基2-叠氮基-4,6-O-亚苄基-2-脱氧-3-O-（甲基2,3,4-三-O-乙酰基-甲基α-L-idopyranosyluronate）-β-D-吡喃半乳糖苷。在三氟甲硅烷基三甲基甲硅烷基酯的存在下，使用（2,3,4-三-O-乙酰基-α-L-氨基吡喃基三氯乙酰亚氨酸甲酯）尿酸甲酯作为糖基供体将收率提高至68％。用氰基硼氢化钠区域选择性地打开亚苄基，然后依次用三氧化硫-三甲胺络合物进行O-硫酸化，皂化，催化氢解和选择性的N-乙酰化得到甲基2-乙酰氨基-2-脱氧-3-O-（α-L-氨基吡喃糖基糖醛酸）-4-O-磺基-β-D-吡喃半乳糖苷的二钠盐。2-叠氮基-4,6-O-亚苄基-2-脱氧-β-D-吡喃半乳糖苷与（2

  DOI：

  10.1016/0008-6215(89)85086-4
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-azido-2-deoxy-α/β-D-galactopyranosyl nitrate 在 sodium 、 zinc(II) chloride 作用下， 以 甲醇 为溶剂， 反应 109.0h， 生成 methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-galactopyranoside
  参考文献：
  名称：

  Bukowski, Ralph; Morris, Laura M.; Woods, Robert J., European Journal of Organic Chemistry, 2001, # 14, p. 2697 - 2705

  摘要：

  DOI：

文献信息

• l-Iduronic acid derivatives as glycosyl donors
  作者：Christine Tabeur、Françoise Machetto、Jean-Maurice Mallet、Philippe Duchaussoy、Maurice Petitou、Pierre Sinaÿ

  DOI：10.1016/0008-6215(95)00346-0

  日期：1996.2

  O-[Methyl (2-O-acetyl-3-O-benzyl-4-O-levulinyl-alpha, and beta-L-idopyranosid)uronate] trichloroacetimidate and the corresponding n-pentenyl glycosides are efficient L-iduronic acid glycosyl donors. Both have been used for the high-yielding synthesis of basic disaccharide blocks which are useful for the subsequent synthesis of complex oligosaccharides related to heparin/heparan sulfate, and dermatan

  O-[（2-O-乙酰基-3-O-苄基-4-O-乙酰丙酰基-α-甲基和β-L-idopyranosid）尿酸甲酯]三氯乙亚胺酸酯和相应的n-戊烯基糖苷是有效的L-艾杜糖酸糖基供体。两者均已用于碱性二糖嵌段的高产率合成，其对于随后合成与肝素/硫酸乙酰肝素和硫酸皮肤素有关的复杂寡糖是有用的。相反，相应的硫代乙基糖苷，硫代苯基糖苷和氟化物未产生预期的二糖。
• 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。
• Synthesis, Conformation and T-Helper Cell Stimulation of an O-Linked Glycopeptide Epitope Containing Extended Carbohydrate Side-Chains
  作者：Mare Cudic、Hildegund C.J Ertl、Laszlo Otvos

  DOI：10.1016/s0968-0896(02)00388-7

  日期：2002.12

  carry extended sugar chains, we prepared Fmoc-Ser/Thr-OPfp building blocks containing alpha- and beta-linked linear tri- and heptasaccharides. Peptide 31D was synthesized with the complex carbohydrates attached to Thr4, and the T-helper cell activity of the glycopeptides was determined. Addition of alpha-linked carbohydrates, that mimic most of the natural O-linked glycoproteins, resulted in a major

  为了回答T细胞是否具有免疫显性蛋白片段识别糖基化抗原的问题，我们合成了一系列与肽31D相对应的糖肽，肽31D是狂犬病毒核蛋白的主要T辅助细胞表位。已知该表位的Thr4允许以α-或β-异头构型的单糖或二糖侧链取代，而不会干扰MHC结合。为了模拟携带延伸糖链的天然糖蛋白片段，我们制备了含有α-和β-连接的线性三糖和七糖的Fmoc-Ser / Thr-OPfp结构单元。合成了具有附着在Thr4上的复合碳水化合物的肽31D，并确定了糖肽的T辅助细胞活性。添加α-连接的碳水化合物，模仿大多数天然O-连接的糖蛋白，导致糖长度依赖性方式的T细胞刺激能力大大下降。相反，模仿β-连接的糖肽的胞质糖蛋白保留了它们的T细胞刺激活性，含三糖的类似物几乎与未糖基化的肽一样有效。当将肽与稀释的人血清预孵育后，所有肽均失去了刺激9C5.D8-H杂交瘤的能力。这些发现表明（i）与胞质糖基化相反，将长O-连接的碳水化合物掺
• Synthesis of the building blocks N^α-Fmoc-O-[α-<scp>D</scp>-Ac₃GalN₃p-(1<b>→</b>3)-α-<scp>D</scp>-Ac₂GalN₃p]-Thr-OPfp and N^α-Fmoc-O-[α-<scp>D</scp>-Ac₃GalN₃p-(1<b>→</b>6)-α-<scp>D</scp>-Ac₂GalN₃p]-Thr-OPfp and their application in the solid phase glycopeptide synthesis of core 5 and core 7 mucin O-glycopeptides
  作者：Sandrine Rio-Anneheim、Hans Paulsen、Morten Meldal、Klaus Bock

  DOI：10.1039/p19950001071

  日期：——

  The structures alpha-D-GalNAc-( 1-->3)-alpha-D-GalNAc-(1-->O)-L-Thr and alpha-D-GalNAc-(1-->6)-alpha-D-GalNAc-(1-->O)-L-Thr are present as cores 5 and 7 of the mucin-type glycoproteins. The preparation of the corresponding building blocks 10 and 15 is described. Compounds 10 and 15 can be used directly in a multiple-column solid-phase glycopeptide peptide synthesis. In the resulting peptides the azido groups are reduced and acetylated on the solid support. The products are cleaved from the resin and the carbohydrate part is deprotected. A series of 20 O-glycopeptides has been prepared.
• ——
  作者：Tarikere L. Gururaja、Paloth Venugopalan、Michael J. Levine

  DOI：10.1023/a:1021864511771

  日期：——

  Synthesis of methyl 2-azido-2-deoxy-4,6-O-benzylidene-beta-D-galactopyranoside (1), one of the key components in the synthesis of O-glycoamino acids, was undertaken in order to synthesize Tn and TF(3) antigen building blocks. In pursuit of an alternative approach, benzylidenation of the crude D-galactal (2a) afforded methyl 2-deoxy-4,6-O-benzylidene-alpha-D-galactopyranoside (3c) and 3,4-O-benzylidene-D-galactal (3b) besides the expected 4,6-O-benzylidene-D-galactal (3a). Formation of compound 3c was explained based on the presence of methyl 2 deoxy-alpha-D-galactopyranoside (2b) isomer and/or trace amount of methanol in the crude mixture of deacetylated product of 2 prior to benzylidenation. On the other hand, formation of 3b in substantial quantities appears to be a thermodynamically controlled product and its formation is found to be common during prolonged Lewis-acid catalyzed benzylidenation reaction. Crystal structures of these important and useful precursors were deduced by X-ray diffraction methods to enumerate their complete molecular structure as well as to understand the effect of the cyclic acetal on the pyranose ring conformation. Compound 1 crystallizes in the orthorhombic space group P2(1)2(1)2(1) With cell dimensions a = 5.058(7), b = 12.766(7), c = 22.557(7) Angstrom; 3b crystallizes in the hexagonal space group P6(1) with cell dimensions a = 18.265(4), b = 18.265(3), c = 6.323(2) Angstrom; 3c crystallizes in the monoclinic space group P2(1) with cell dimensions a = 10.614(3), b = 4.963(2), c = 12.730(3) Angstrom, and beta = 95.47(3)degrees.