methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-vinyl-α-D-galactopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside | 352020-87-2

• 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-vinyl-α-D-galactopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside
• 英文别名: (2S,3R,4S,5S,6R)-2-ethenyl-2-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 352020-87-2
• 化学式: C₆₄H₆₈O₁₁
• 分子量: 1013.24
• InChiKey: UOZIDEDLEPWSKJ-YUCRRGNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.9
• 重原子数：
  75
• 可旋转键数：
  27
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.31
• 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-vinyl-α-D-galactopyranosyl)-(1'->6)-2,3,4-tri-O-benzyl-α-D-glucoside 在 sodium hydroxide 、 臭氧 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 以30.2%的产率得到methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-methoxycarbonyl-α-D-galactopyranosyl)-(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
• 作为产物：
  描述：

  2,3,4,6-四-O-(苯基甲基)-D-半乳糖酸 D-内酯 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 methyl O-(2',3',4',6'-tetra-O-benzyl-1'-C-vinyl-α-D-galactopyranosyl)-(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

• Different reaction routes found in acid-catalyzed glycosylation of endo- and exo-glycals: competition between Ferrier rearrangement and protonation
  作者：Hui-Chang Lin、Wen-Ping Du、Chih-Chun Chang、Chun-Hung Lin

  DOI：10.1016/j.tetlet.2005.05.061

  日期：2005.7

  products is often obtained resulting from Ferrier rearrangement and protonation. The former reaction exclusively takes place with the t-butyl carbonate or hydroxyl substituent at the C3 position of endo-glycals, while the latter mainly occurs in the glycosylation of exo-glycals with allyl benzyl ether or acetate. In addition to the substituent effect, protecting groups are critical to determine the

  内-和外-糖的酸介导的糖基化已经以良好或优异的产率进行，其中经常由于费里耳重排和质子化而获得两种产物的混合物。前者反应只发生与吨丁基碳酸酯或在C3位羟基取代基内切-glycals，而后者主要发生在糖基化外型-glycals与烯丙基苄基醚或乙酸盐。除取代基作用外，保护基对于确定活性和有利的反应途径也至关重要。此外，该方法适用于O-，C-和N-亲核试剂。
• Stereoselective Glycosylation of <i>exo</i>-Glycals Accelerated by Ferrier-Type Rearrangement
  作者：Hui-Chang Lin、Wen-Bin Yang、Yu-Feng Gu、Chen、Chung-Yi Wu、Chun-Hung Lin

  DOI：10.1021/ol034130z

  日期：2003.4.1

  [GRAPHIC]Owing to the driving force of the Ferrier-type rearrangement, the exo-glycals are highly reactive with various alcohols to afford glycosides and glycoconjugates with exclusive alpha-configuration. The resulting vinyl group in these glycosylation products can be further elaborated for general applications, including the synthesis of spiro derivatives and glycosylation of 2-ketoaldonic acids.
• 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.