3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-β-D-galactopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose | 249511-73-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-β-D-galactopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
• 英文别名: 3,4-O-isopropylidene-6-O-(methoxydimethyl)-methyl-D-galactopyranosyl-(1-> 6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose；(3aS,4R,6R,7R,7aR)-4-(2-methoxypropan-2-yloxymethyl)-2,2-dimethyl-6-[[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methoxy]-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-ol
• CAS: 249511-73-7
• 化学式: C₂₅H₄₂O₁₂
• 分子量: 534.601
• InChiKey: RIQPFTZYIRALAC-NCTAMAIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  37
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  122
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-β-D-galactopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose 在 sodium hydride 、 溶剂黄146 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 6.0h， 生成 3,4-O-isopropylidene-6-O-(p-methoxybenzyl)-2-O-(2-naphthyl)methyl-β-D-galactopyranosyl-(1→6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  在对甲氧基苄基存在下通过催化氢化选择性去除（2-萘基）甲基保护基

  摘要：

  在对甲氧基苄基 (PMB)、苄基和亚苄基存在下，(2-萘基)甲基 (NAP) 基团的选择性裂解是通过一系列单糖的催化氢化实现的。在二糖水平上，PMB 基团在 NAP 氢解时是稳定的，但是，观察到苄基醚功能的部分裂解。

  DOI：

  10.3998/ark.5550190.0013.526
• 作为产物：
  描述：

  2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose 在 sodium methylate 、 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 反应 2.5h， 生成 3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-β-D-galactopyranosyl-(1->6)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  Scope and limitation of the application of the (methoxydimethyl)methyl group in the synthesis of 2′-O-, 6′-O- and 2′,6′-di-O-(α-l-arabinofuranosyl)-β-d-galactopyranosyl-(1→6)-d-galactoses

  摘要：

  For the characterisation of the anticipated epitope of an arabinogalactan, isolated from the extract of Echinacea purpurea, the trisaccharide alpha-L-Araf-(1 --> 2)-beta-D-Galp-(1 --> 6)-D-Gal was synthesized. The easily available 3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-beta-D-galactopyranosyl- (1 --> 6)-1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose having the OH-2' free served as aglycone upon direct arabinosylation at the 2' position under Helferich conditions. The formed HgBr2 cleaved the acid sensitive protecting group at position 6', but under basic conditions the desired, fully protected trisaccharide, or its symmetrical dimerization derivative linked 6'- to 6'-position via an isopropylidene bridge, could be obtained. An alternative route involved arabinosylation of a hepta-O-acetylated digalactose with free OH-2'. Two other oligosaccharides, namely, alpha-L-Araf-(1 --> 6)-beta-D-Galp-(1 --> 6)-D-Gal and (alpha-L-Araf)(2)-(1 --> 2,6)-beta-D-Galp-(1 --> 6)-D-Gal were also synthesized and characterised. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(99)00094-4

文献信息

• Successful Combination of (Methoxydimethyl)methyl (MIP) and (2-Naphthyl)methyl (NAP) Ethers for the Synthesis of Arabinogalactan-Type Oligosaccharides
  作者：Magdolna Csávás、Anikó Borbás、László Szilágyi、András Lipták

  DOI：10.1055/s-2002-31893

  日期：——

  In order to characterise the presumed epitopes of arabinogalactans, isolated from the extract of the cell-cultured Echinacea purpurea, two oligosaccharides were synthesized. The whole synthetic route was based on the successful combination of the (methoxydimethyl)methyl (MIP) and the (2-naphthyl)methyl ether (NAP) protecting groups. A β-(1→6)-linked trigalactoside was prepared, which contained a NAP ether at position 2′.This protecting group was selectively removed using either DDQ or Pd-C/H2 and the acceptor was ready for further glycosylation.We have used two arabinofuranosyl donor compounds: 2,3,5-tri-O-acetyl arabinofuranosyl trichloroacetimidate and a peracetylated α-(1→5)-linked diarabinofuranosyl trichloroacetimidate. For the deprotection of the tetra- and pentasaccharides a common procedure was used. All of the synthesized compounds were characterized by 1H and 13C NMR spectroscopy, as well as by MALDI-TOF mass-spectrometry.

  为了确定从细胞培养的紫锥菊提取物中分离出来的阿拉伯半乳聚糖的假定表位特征，我们合成了两种寡糖。整个合成路线基于（甲氧基二甲基）甲基（MIP）和（2-萘基）甲基醚（NAP）保护基团的成功结合。使用 DDQ 或 Pd-C/H2 可以选择性地去除该保护基团，然后就可以将受体进一步糖基化。我们使用了两种阿拉伯呋喃糖基供体化合物：2,3,5-三-O-乙酰基阿拉伯呋喃糖基三氯乙酰亚氨酸酯和过乙酰化的δ-（1→5）-连接二阿拉伯呋喃糖基三氯乙酰亚氨酸酯。四糖和五糖的脱保护采用了相同的程序。所有合成的化合物都通过 1H 和 13C NMR 光谱以及 MALDI-TOF 质谱法进行了表征。
• Scope and limitation of the application of the (methoxydimethyl)methyl group in the synthesis of 2′-O-, 6′-O- and 2′,6′-di-O-(α-l-arabinofuranosyl)-β-d-galactopyranosyl-(1→6)-d-galactoses
  作者：Anikó Borbás、Lóránt Jánossy、András Lipták

  DOI：10.1016/s0008-6215(99)00094-4

  日期：1999.5

  For the characterisation of the anticipated epitope of an arabinogalactan, isolated from the extract of Echinacea purpurea, the trisaccharide alpha-L-Araf-(1 --> 2)-beta-D-Galp-(1 --> 6)-D-Gal was synthesized. The easily available 3,4-O-isopropylidene-6-O-(methoxydimethyl)methyl-beta-D-galactopyranosyl- (1 --> 6)-1,2:3,4-di-O-isopropylidene-alpha-D-galactopyranose having the OH-2' free served as aglycone upon direct arabinosylation at the 2' position under Helferich conditions. The formed HgBr2 cleaved the acid sensitive protecting group at position 6', but under basic conditions the desired, fully protected trisaccharide, or its symmetrical dimerization derivative linked 6'- to 6'-position via an isopropylidene bridge, could be obtained. An alternative route involved arabinosylation of a hepta-O-acetylated digalactose with free OH-2'. Two other oligosaccharides, namely, alpha-L-Araf-(1 --> 6)-beta-D-Galp-(1 --> 6)-D-Gal and (alpha-L-Araf)(2)-(1 --> 2,6)-beta-D-Galp-(1 --> 6)-D-Gal were also synthesized and characterised. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Selective removal of the (2-naphthyl)methyl protecting group in the presence of p-methoxybenzyl group by catalytic hydrogenation
  作者：László Lázár、Lóránt Jánossy、Magdolna Csávás、Mihály Herczeg、Anikó Borbása、Sándor Antus

  DOI：10.3998/ark.5550190.0013.526

  日期：——

  Selective cleavage of the (2-naphthyl)methyl (NAP) group in the presence of p-methoxybenzyl (PMB), benzyl and benzylidene groups was achieved by catalytic hydrogenation with a series of monosaccharides. At a disaccharide level, the PMB group was stable upon hydrogenolysis of the NAP, however, partial cleavage of benzyl ether functions was observed.

  在对甲氧基苄基 (PMB)、苄基和亚苄基存在下，(2-萘基)甲基 (NAP) 基团的选择性裂解是通过一系列单糖的催化氢化实现的。在二糖水平上，PMB 基团在 NAP 氢解时是稳定的，但是，观察到苄基醚功能的部分裂解。