Methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(methyl 2,3,4-tri-O-benzyl-β-D-glucopyranosyluronate)-α-D-mannopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(methyl 2,3,4-tri-O-benzyl-β-D-glucopyranosyluronate)-α-D-mannopyranoside
• 英文别名: methyl (2S,3S,4S,5R,6R)-6-[[(2R,4aR,6S,7S,8S,8aR)-6-methoxy-2-phenyl-8-phenylmethoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]oxy]-3,4,5-tris(phenylmethoxy)oxane-2-carboxylate
• 化学式: C₄₉H₅₂O₁₂
• 分子量: 832.945
• InChiKey: TVLZXYIOOBCURE-VTCGJANFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  61
• 可旋转键数：
  18
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  119
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 吡啶 、 重铬酸吡啶 、 4 A molecular sieve 、 DMTST 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 生成 Methyl 3-O-benzyl-4,6-O-benzylidene-2-O-(methyl 2,3,4-tri-O-benzyl-β-D-glucopyranosyluronate)-α-D-mannopyranoside
  参考文献：
  名称：

  Synthesis of Methyl (Ethyl 2-O-acyl-3,4-di-O-benzyl-1-thio-.beta.-D-glucopyranosid)uronates and Evaluation of Their Use as Reactive .beta.-Selective Glucuronic Acid Donors

  摘要：

  The synthesis of derivatives of methyl (ethyl 2-0-acyl-3,4-di-O-benzyl-1-thio-beta-D-glucopyranosid)-uronate with different ester groups (acetyl, benzoyl, pivaloyl, and anisoyl) at O-2 is described. The synthesis proceeds via a two-step oxidation (DMSO/DCC followed by PDC/MeOH) of C-6 on a suitably protected glucose derivative to give directly the methyl glucuronic ester without affecting the thioglycoside. The thioglucuronides were tested as donors in coupling reactions with unreactive carbohydrate alcohols using dimethyl(methylthio)sulfonium triflate (DMTST) as promoter, Due to the activating benzyl protecting groups at O-3 and -4, the sluggishness of fully acylated glucuronic acid donors could be overcome and glucuronide disaccharides were produced in fair to good yields. The glucuronides were obtained with the desired P-configuration because of the participating group at O-2. Among the different ester groups tried, the benzoyl group was found to give the highest yield in the couplings.

  DOI：

  10.1021/jo00112a046

文献信息

• Synthesis of Methyl (Ethyl 2-O-acyl-3,4-di-O-benzyl-1-thio-.beta.-D-glucopyranosid)uronates and Evaluation of Their Use as Reactive .beta.-Selective Glucuronic Acid Donors
  作者：Per J. Garegg、Lars Olsson、Stefan Oscarson

  DOI：10.1021/jo00112a046

  日期：1995.4

  The synthesis of derivatives of methyl (ethyl 2-0-acyl-3,4-di-O-benzyl-1-thio-beta-D-glucopyranosid)-uronate with different ester groups (acetyl, benzoyl, pivaloyl, and anisoyl) at O-2 is described. The synthesis proceeds via a two-step oxidation (DMSO/DCC followed by PDC/MeOH) of C-6 on a suitably protected glucose derivative to give directly the methyl glucuronic ester without affecting the thioglycoside. The thioglucuronides were tested as donors in coupling reactions with unreactive carbohydrate alcohols using dimethyl(methylthio)sulfonium triflate (DMTST) as promoter, Due to the activating benzyl protecting groups at O-3 and -4, the sluggishness of fully acylated glucuronic acid donors could be overcome and glucuronide disaccharides were produced in fair to good yields. The glucuronides were obtained with the desired P-configuration because of the participating group at O-2. Among the different ester groups tried, the benzoyl group was found to give the highest yield in the couplings.