methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside | 13035-24-0

• 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 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside
• 英文别名: methyl 4,6-O-benzylidene-2,3-di-O-benzyl-β-D-glucopyranoside；Methyl-2,3-di-O-benzyl-4,6-O-benzyliden-β-D-glucopyranosid；Methyl-4,6-O-benzyliden-2,3-di-O-benzyl-β-D-glucopyranosid；2,3-Dibenzyl-4,6-O-benzyliden-methyl-α-D-glucopyranosid；Methyl 2,3-di-o-benzyl-4,6-o-benzylidene-beta-d-glucopyranoside；(4aR,6R,7R,8S,8aR)-6-methoxy-2-phenyl-7,8-bis(phenylmethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine
• CAS: 13035-24-0
• 化学式: C₂₈H₃₀O₆
• 分子量: 462.543
• InChiKey: CVHUOBYFXKHVJR-ODBZVETESA-N

物化性质

• 沸点：
  585.4±50.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 methyl 2,3-di-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  Enantioselective alkylation of aldehydes using dialkylzincs catalyzed by simple chiral diols derived from naturally occurring monosaccharides

  摘要：

  Enantioselective alkylation of aldehydes was achieved in up to 84% ee using dialkylzincs catalyzed by simple dials derived from naturally occurring monosaccharides. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.03.090
• 作为产物：
  描述：

  甲基 Β-D-吡喃葡萄糖苷 在 sodium hydride 、 对甲苯磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 18.25h， 生成 methyl 2,3-di-O-benzyl-4,6-O-benzylidene-β-D-glucopyranoside
  参考文献：
  名称：

  O-β-D-甘露糖基-(1→4)-O-α-D-甘露糖基-(1→3)-L-鼠李糖和O-(2-乙酰氨基-2-脱氧-β-D-甘露糖基)-的合成(1→4)-O-α-D-半乳糖基-(1→4)-D-半乳糖通过使用 2-O-Acetyl-3,4,6-tri-O-benzyl-D 的原位激活糖基化-葡萄糖

  摘要：

  O-β-D-吡喃甘露糖基-(1→4)-O-α-D-吡喃甘露糖基-(1→3)-L-吡喃鼠李糖，一种三糖，包括越南Bulkholderia vietnamiensis的O-特异性多糖(OSP)的重复单元LMG 6988 菌株，和 O-(2-乙酰氨基-2-脱氧-β-D-吡喃甘露糖基)-(1→4)-O-α-D-吡喃半乳糖基-(1→4)-D-吡喃半乳糖，一种三糖，包括使用 2-O-乙酰基-3,4,6-三-O-苄基-D-吡喃葡萄糖 (2ATBG) 和试剂通过原位激活糖基化合成鲍曼不动杆菌血清组 O18 的 OSP 重复单元对硝基苯磺酰氯、三氟甲磺酸银和 1,8-二氮杂双环[5.4.0]十一碳-7-烯的混合物，以及相关系统。2ATBG、烯丙基 2,3,6-三-O-苄基-α-D-吡喃半乳糖苷、苄基 2,3,6-三-O-苄基-α-D-吡喃半乳糖苷和 2-叠氮基-3 的新合成，描述了 4,6-三-O-苄基-2-脱氧-D-吡喃甘露糖。

  DOI：

  10.1246/bcsj.76.1603

文献信息

• Temperature-Controlled Regioselectivity in the Reductive Cleavage of <i>p</i>-Methoxybenzylidene Acetals
  作者：Jesús M. Hernández-Torres、Jihane Achkar、Alexander Wei

  DOI：10.1021/jo048999m

  日期：2004.10.1

  functional groups, including allyl and enol ethers. The presence of water does not interfere with reductive ring opening and may contribute toward in situ generation of H+ as a catalyst for 6-O-PMB ether formation. Reductive cleavage under rigorously aprotic conditions is greatly decelerated, and yields only the 4-O-PMB ether. The temperature-dependent reductive cleavage of the 4,6-acetal can be described in

  可以通过调节反应温度和试剂浓度来调节吡咯型4，6-对-甲氧基亚苄基乙缩醛与BH 3 / Bu 2 BOTf在THF中的区域选择性开环。在0还原裂解℃下导致的专属形成4- ø - p甲氧基苄基（PMB）醚，而反应在-78℃下产生的6- ö -PMB醚以高收率。观察到后一种条件与包括烯丙基醚和烯醇醚在内的各种酸敏感性官能团相容。水的存在不会干扰还原性开环，并且可能有助于原位生成H +作为6- O的催化剂-PMB醚的形成。在严格非质子条件下的还原裂解被大大减速，并且仅产生4- O- PMB醚。4,6-乙缩醛的温度依赖性还原裂解可通过动力学与热力学控制来描述：在较高温度下，更易接近的O-6的路易斯酸配位是有利的，而更碱性但空间受限的质子化O-4在低温下占主导地位。
• A new one-pot synthesis of Gb3 and isoGb3 trisaccharide analogues
  作者：Changning Wang、Qin Li、Haisheng Wang、Li-He Zhang、Xin-Shan Ye

  DOI：10.1016/j.tet.2006.09.058

  日期：2006.12

  Gb(3) and isoGb(3) are both biologically important oligosaccharides. A new efficient synthesis of Gb(3) and isoGb(3) trisaccharide analogues has been achieved by one-pot sequential glycosylation strategy starting from simple monosaccharide building blocks promoted by N-(phenylthio)-epsilon-caprolactam at room temperature. (c) 2006 Elsevier Ltd. All rights reserved.
• Chemistry of 4,6-<i>O</i>-Benzylidene-<scp>d</scp>-glycopyranosyl Triflates:  Contrasting Behavior between the Gluco and Manno Series
  作者：David Crich、Weiling Cai

  DOI：10.1021/jo990243d

  日期：1999.6.1

  Activation of either anomer of S-phenyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-D-glucopyranoside with triflic anhydride in dichloromethane at -78 degrees C in the presence of 2,6-di-tert-butyl-4-methylpyridine affords a highly active glycosylating species which, on addition of alcohols, provides cl-glucosides with high selectivity. This selectivity stands in stark contrast to the analogous mannopyranoside series, which affords the beta-mannosides with excellent selectivity under the same conditions. Low-temperature NMR experiments support the notion that a glucosyl triflate is formed in the initial activation step. Possible reasons for the diverging stereoselectivity in the gluco and manno series are discussed.
• Gas phase glycosidic cleavage of oxynions from alkyl glycosides
  作者：Jean-Claude Prome、Hélène Aurelle、Danielle Prome、Arlette Savagnac

  DOI：10.1002/oms.1210220104

  日期：1987.1

  AbstractThe oxyanion [MH]− from several methylglycosides were generated by fast atom bombardment and their decomposition was studied by mass‐analysed ion kinetic energy spectrometry. The main decomposition pathway is the loss of methanol. The hydroxylic hydrogen arises by proton transfer from the hydroxyl groups of the sugar. In the gluco‐series, no anomeric effect is found. The absence of either the hydroxyl groups at C‐2 or C‐6 does not inhibit the glycosidic cleavage. However, the blocking of both the hydroxyl groups at C‐4 and C‐6, by a benzylidene group or two methyl groups, inhibit completely the glycosidic cleavage. From these results, it is proposed that the glycosidic cleavage occurs after opening the sugar ring by a vicinal attack of an oxyanion at C‐6 or C‐4 to the C‐5 carbon atom. Then, the ionized hemi‐acetals fragment into a methanolate anion and a 5,6‐ or 4,5‐anhydrosugar which exchange another proton before their separation into charged and neutral species.
• Preparation of two methyl deoxyfluoro-β-d-galactopyranosides, and their interaction with galactan-specific immunoglobulin A 1539 (fab′)
  作者：Yitzhak Ittah、Cornelis P.J. Glaudemans

  DOI：10.1016/s0008-6215(00)85575-5

  日期：1981.9

  Methyl 2-deoxy-2-fluoro-beta-D-glactopyranoside (2) and methyl 4-deoxy-4-fluoro-beta-D-glactopyranoside (7) have been prepared, and the possibility of their binding to (1 leads to 6)-beta-D-galactopyranan-specific immunoglobulin A J539 (Fab') has been investigated. Compound 2 does not show binding, whereas 7 does. It appears that the 2-hydroxyl group of methyl beta-D-galactopyranoside may take part in hydrogen bonding to the protein.