1,6-anhydro-2,3-O-benzylidene-β-D-mannopyranose | 5349-10-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 1,6-anhydro-2,3-O-benzylidene-β-D-mannopyranose
• 英文别名: (1R,2S,6S,7R,8R)-4-phenyl-3,5,10,11-tetraoxatricyclo[6.2.1.02,6]undecan-7-ol
• CAS: 5349-10-0
• 化学式: C₁₃H₁₄O₅
• 分子量: 250.251
• InChiKey: JOPKJLNPGQZOJZ-FKBPTDFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1,6-anhydro-2,3-O-benzylidene-β-D-mannopyranose 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 O-(β-D-Galactopyranosyl)-(1->4)-1,6-anhydro-2,3-O-endo/exo-benzylidene-β-D-mannopyranose
  参考文献：
  名称：

  Oligosaccharides Structurally Related to E-Selectin Ligands Are Inhibitors of Neural Cell Division: Synthesis, Conformational Analysis, and Biological Activity

  摘要：

  Oligosaccharides containing either the Lewis X trisaccharide fragment (3-fucosyl-N-acetyllactosamine) with N-acetylgalactosamine at the C-3 position of the galactose unit (compound 2 and the 1,6-anhydro derivative 5) or the trisaccharide 3-fucosyllactose having N-acetylneuraminic and sulfate groups at the C-3; position of the galactose (3 and 4, respectively) have been synthesized and tested for the ability to inhibit the division of astrocytes and transformed cell lines and their conformation studied. Compounds 3 and Care structurally related to sulfated Lewis X and sialyl Lewis X which are known to be recognized by E-selectin. The synthesis of 2 and 5 was accomplished by an original route starting from 1,6-anhydro-beta-D-mannose, while 3 and 4 were efficiently prepared from methyl beta-lactoside. The conformational analysis has been carried out using NMR, molecular mechanics, and molecular dynamics. Compounds 2-4 were inhibitors in all cell types tested showing ID50 values in the mu M range; however, 5 showed a marked decrease in the ID50 value on astrocytes emphasizing upon the importance of the relative orientation of the fucosyl unit. Tetrasaccharide 3 was the most active on astrocytes (ID50 = 35 mu M), whereas the sulfate 4 was the best inhibitor on tumor-forming C6 glioma cells (ID50 = 79 mu M).

  DOI：

  10.1021/jo00111a008
• 作为产物：
  描述：

  甘露糖 在 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 50.0 ℃ 、4.0 kPa 条件下， 反应 3.0h， 生成 1,6-anhydro-2,3-O-benzylidene-β-D-mannopyranose
  参考文献：
  名称：

  N-溴代琥珀酰亚胺的丙烯腈-己糖苷的构型以及N-乙酰基-1-霉菌胺的合成和合成

  摘要：

  摘要通过同时糖化和乙缩醛缩醛化的新方法，制备了甲基2,3：5,6-二-O-亚苄基-α-d-甘露呋喃糖苷和甲基2,3-O-亚苄基-α-1-L-呋喃呋喃糖苷。 -甘露糖和l-鼠李糖。用N-溴代琥珀酰亚胺处理这些化合物和1，6-脱水-2，3-O-亚苄基-d-甘露糖，通过缩醛环的区域特异性开放仅得到3-溴化合物。因此，从鼠李糖开始，以七个步骤制备了N-乙酰基-1-霉豆胺（3-氨基-3,6-二脱氧-1-甘露糖），总产率为32％。

  DOI：

  10.1016/s0008-6215(00)84674-1

文献信息

• Reaction of butyllithium with benzylidene acetals of aldopyranosides and 1,5-anhydroalditols
  作者：Derek Horton、Wolfgang Weckerle

  DOI：10.1016/0008-6215(88)85099-7

  日期：1988.3

  butyllithium selectively cleaves 5-membered benzylidene acetals (1,3-dioxolane ring) leaving the 6-membered analogs (1,3-dioxane ring) intact in aldopyranoside and 1,5-anhydroalditol derivatives. The usual course of the reaction involves expulsion of the elements of benzaldehyde to give an enolate anion and thence a vicinal deoxyketone. The reaction is strongly regioselective and may be interpreted as proceeding

  摘要在合适的条件下，丁基锂选择性地裂解5元亚苄基缩醛（1,3-二氧戊环），而6元类似物（1,3-二氧六环）则完整保留在醛吡喃糖苷和1,5-脱水醛醇衍生物中。该反应的通常过程包括排出苯甲醛的元素以产生烯醇式阴离子，并因此得到邻位的脱氧酮。该反应具有强烈的区域选择性，可以解释为通过在也是1，3-二氧戊环环的一部分的糖环上提取准轴向氢原子而进行。因此，具有相当大的合成效用的受控路线是可行的。在某些情况下，存在替代的反应途径，该反应途径包括将苯甲酸酯阴离子的元素排出，并形成烯烃，即相应的环不饱和吡喃糖衍生物。
• Bock; Meldal, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1983, vol. 37, # 9, p. 775 - 783
  作者：Bock、Meldal

  DOI：——

  日期：——
• Synthetic galactomannans with potent anti-HIV activity
  作者：Davaanyam Budragchaa、Shiming Bai、Taisei Kanamoto、Hideki Nakashima、Shuqin Han、Takashi Yoshida

  DOI：10.1016/j.carbpol.2015.04.047

  日期：2015.10

  Ring-opening polymerization of a new 1,6-anhydro disaccharide monomer, 1, 6-anhydro-2, 3-di-O-benzyl-4-O-(2', 3', 4', 6'-tetra-O-benzyl-alpha-D-galactopyranosyl)-alpha-D-rpannopyranose, was carried out using PF5 as a catalyst under high vacuum at -60 degrees C to give galactose branched mannopyranan (synthetic galactomannan), 4-O-alpha-D-galactopyranosyl-(1 -> 6)-alpha-D-mannopyranan, after debenzylation with Na in liquid NH3. The ring-opening copolymerization with 1, 6-anhydro-tri-O-benzyl-alpha-D-mannopyranose in various feeds was also performed to give synthetic galactomannans with various proportions of galactose branches. After sulfation, sulfated synthetic galactomannans were found to have anti-HIV activity and cytotoxicity as high and low as those of standard curdlan and dextran sulfates, respectively, which are potent anti-HIV sulfated polysaccharides with low cytotoxicity. The anti-HIV mechanism of sulfated synthetic galactomannans used by poly-L-lysine as a model peptide of the HIV surface protein was estimated by using SPR, DSL, and zeta potential measurements, revealing the electrostatic interaction between negatively charged sulfate groups and positively charged amino groups. (C) 2015 Elsevier Ltd. All rights reserved.
• Building blocks for the synthesis of glycosyl-myo-inositols involved in the insulin intracellular signalling process
  作者：Amparo Zapata、Manuel Martín-Lomas

  DOI：10.1016/0008-6215(92)85041-w

  日期：1992.10

  Glycosylation of (+/-)-l-0-benzyl-2,3:5,6-di-0-isopropylidene-myo-inositol (4) with 6-O-acetyl-4-O-allyl-2-azido-3-0-benzyl-2-deoxy-beta-D-glucopyranosyl trichloroacetimidate (6) gave the 4-O-(2-amino-2-deoxy-alpha-D-glucopyranosyl)-myo-inositol derivative (9) as a mixture of diastereoisomers which could be resolved by chromatography. Likewise alpha-glycosylation of 4 with 6-0-acetyl-2-azido-3-0-benzoyl-2-de-oxy-4-0-(2,3,4,6-tetra-0-acetyl-beta-D-galactopyranosyl)-D-glucopyranosyl trichloroacetimidate (10) gave the corresponding pseudotrisaccharide derivative 16 as a mixture of diastereomers which could be resolved partially by chromatography. alpha-Glycosylation of enantiomerically pure 2,3:5,6- (18) and 2,3:4,5-di-0-isopropylidene-1-0-menthoxycarbonyl-myo-inositol (19) with 3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-glucopyranosyl trichloroacetimidate (20) gave the pseudodisaccharide derivatives 21 and 22, respectively. Likewise, alpha-glycosylation of 18 with 10 afforded a pseudotrisaccharide derivative (23).
• Oligosaccharides Structurally Related to E-Selectin Ligands Are Inhibitors of Neural Cell Division: Synthesis, Conformational Analysis, and Biological Activity
  作者：Jose M. Coteron、Kamaljit Singh、Juan L. Asensio、Maria Dominguez-Dalda、Alfonso Fernandez-Mayoralas、Jesus Jimenez-Barbero、Manuel Martin-Lomas、Manuel Nieto-Sampedro

  DOI：10.1021/jo00111a008

  日期：1995.3

  Oligosaccharides containing either the Lewis X trisaccharide fragment (3-fucosyl-N-acetyllactosamine) with N-acetylgalactosamine at the C-3 position of the galactose unit (compound 2 and the 1,6-anhydro derivative 5) or the trisaccharide 3-fucosyllactose having N-acetylneuraminic and sulfate groups at the C-3; position of the galactose (3 and 4, respectively) have been synthesized and tested for the ability to inhibit the division of astrocytes and transformed cell lines and their conformation studied. Compounds 3 and Care structurally related to sulfated Lewis X and sialyl Lewis X which are known to be recognized by E-selectin. The synthesis of 2 and 5 was accomplished by an original route starting from 1,6-anhydro-beta-D-mannose, while 3 and 4 were efficiently prepared from methyl beta-lactoside. The conformational analysis has been carried out using NMR, molecular mechanics, and molecular dynamics. Compounds 2-4 were inhibitors in all cell types tested showing ID50 values in the mu M range; however, 5 showed a marked decrease in the ID50 value on astrocytes emphasizing upon the importance of the relative orientation of the fucosyl unit. Tetrasaccharide 3 was the most active on astrocytes (ID50 = 35 mu M), whereas the sulfate 4 was the best inhibitor on tumor-forming C6 glioma cells (ID50 = 79 mu M).