methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-methyl-α-D-glucopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside | 352020-79-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-methyl-α-D-glucopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside
• 英文别名: methyl O-(1'-C-methyl-2',3',4',6'-tetra-O-benzyl-α-D-glucopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside；Bn(-3)[Bn(-4)][Bn(-5)][Bn(-7)]1-deoxy-D-glcHept2ulo(a2-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；(2S,3R,4S,5R,6R)-2-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-2-methyl-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 352020-79-2
• 化学式: C₆₃H₆₈O₁₁
• 分子量: 1001.23
• InChiKey: SYXZZQKHMLOKBJ-BUTUYZQPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.7
• 重原子数：
  74
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-methyl-α-D-glucopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside 在 palladium dihydroxide 三氟甲磺酸 、 4 A molecular sieve 、 氢气 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 27.0h， 生成 methyl O-(1'-C-methyl-α-D-glucopyranosyl)-(1->4)-α-D-glucoside
  参考文献：
  名称：

  以1-亚甲基糖为糖基供体的新型1' - C-甲基-α - O-二糖的高效合成

  摘要：

  首先通过直接路易斯酸催化用作糖基供体的1-亚甲基糖的O-糖基化反应，合成了一系列新的1' - C-甲基-α-二糖。所述Ô -glycosidation得到立体有择相应的1'-甲基α- ö -glycosides其构型暂时由NMR谱，COSY和C-H分配耦合常数3 Ĵ H-2'中，Me-1' 。乙酰基保护的1-亚甲基糖的O-糖基化表明C-2- O处的乙酰基 由于形成叔氧碳鎓离子作为稳定的中间体，因此通过邻近基团的参与，该位置不能有效地控制产物的立体化学。

  DOI：

  10.1016/s0040-4020(01)00319-2
• 作为产物：
  描述：

  2,3,4,6-tetra-O-benzyl-1-C-methyl-α-D-glucopyranose 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 生成 methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-methyl-α-D-glucopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside
  参考文献：
  名称：

  A facile synthesis of 1′-C-alkyl-α-disaccharides from 1-C-alkyl-hexopyranoses and methyl 1-C-methyl-hexopyranosides

  摘要：

  Direct O-glycosidations using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-hexopyranoses as the glycosyl donors were carried out with a catalytic amount (0.2 equiv.) of trimethylsilyl trifluoromethanesulfonate (TMSOTf). The glycosidations proceeded alpha -stereoselectively and furnished the corresponding 1'-C-alkyl-alpha -disaccharides in 71-90% yields. The O-transglycosidations from the benzylated and acetylated methyl I-C-methyl-or-hexopyranosides to the corresponding 1'-C-methyl-alpha -O-disaccharides were also examined, respectively. These transglycosidations took place on alpha -stereoselectivity and provided the 1'-C-methyl-alpha -O-disaccharides as the sole products, implying that no neighboring group participation occured in the reactions. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00321-0

文献信息

• Synthesis of 1-deoxyhept-2-ulosyl-glycono-1,5-lactone utilizing α-selective O-glycosidation of 2,6-anhydro-1-deoxy-d-hept-1-enitols
  作者：Rie Namme、Takashi Mitsugi、Hideyo Takahashi、Moto Shiro、Shiro Ikegami

  DOI：10.1016/j.tet.2006.07.032

  日期：2006.9

  A series of 1-deoxy-heptulo-2-pyranosyl-glycono-1,5-lactones were synthesized utilizing completely a-selective O-glycosidation of heptenitols. Anomeric configuration of the products was confirmed by (3)J(C,H) coupling measurement and X-ray crystal structural analysis. The benzyl-protected ketosyl saccharides were partly unstable, and glycosidic linkage was prone to cleave under the usual debenzylation conditions. To prevent this, we surveyed various additives for the Pd-catalyzed hydrogenation reaction and found that basic alumina was the most effective. (c) 2006 Elsevier Ltd. All rights reserved.
• A facile synthesis of 1′-C-alkyl-α-disaccharides from 1-C-alkyl-hexopyranoses and methyl 1-C-methyl-hexopyranosides
  作者：Xiaoliu Li、Hiro Ohtake、Hideyo Takahashi、Shiro Ikegami

  DOI：10.1016/s0040-4020(01)00321-0

  日期：2001.5

  Direct O-glycosidations using the 1-C-alkyl-2,3,4,6-tetra-O-benzyl-hexopyranoses as the glycosyl donors were carried out with a catalytic amount (0.2 equiv.) of trimethylsilyl trifluoromethanesulfonate (TMSOTf). The glycosidations proceeded alpha -stereoselectively and furnished the corresponding 1'-C-alkyl-alpha -disaccharides in 71-90% yields. The O-transglycosidations from the benzylated and acetylated methyl I-C-methyl-or-hexopyranosides to the corresponding 1'-C-methyl-alpha -O-disaccharides were also examined, respectively. These transglycosidations took place on alpha -stereoselectivity and provided the 1'-C-methyl-alpha -O-disaccharides as the sole products, implying that no neighboring group participation occured in the reactions. (C) 2001 Elsevier Science Ltd. All rights reserved.
• An efficient synthesis of new 1′-C-methyl-α-O-disaccharides using 1-methylenesugars as the glycosyl donors
  作者：Xiaoliu Li、Hiro Ohtake、Hideyo Takahashi、Shiro Ikegami

  DOI：10.1016/s0040-4020(01)00319-2

  日期：2001.5

  A series of new 1′-C-methyl-α-disaccharides were firstly synthesized by the directly Lewis acid-catalyzed O-glycosidation of 1-methylenesugars used as glycosyl donors. The O-glycosidation afforded stereospecifically the corresponding 1′-methyl-α-O-glycosides whose configurations were tentatively assigned by the NMR spectra, COSY and the C–H coupling constant 3JH−2′,Me−1′. The O-glycosidation of the

  首先通过直接路易斯酸催化用作糖基供体的1-亚甲基糖的O-糖基化反应，合成了一系列新的1' - C-甲基-α-二糖。所述Ô -glycosidation得到立体有择相应的1'-甲基α- ö -glycosides其构型暂时由NMR谱，COSY和C-H分配耦合常数3 Ĵ H-2'中，Me-1' 。乙酰基保护的1-亚甲基糖的O-糖基化表明C-2- O处的乙酰基 由于形成叔氧碳鎓离子作为稳定的中间体，因此通过邻近基团的参与，该位置不能有效地控制产物的立体化学。