methyl 4-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: Bz(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Gal(b1-4)[Bn(-2)][Bn(-3)][Bn(-6)]a-Glc1Me；[(2S,3R,4S,5S,6R)-2-[(2R,3R,4S,5R,6S)-6-methoxy-4,5-bis(phenylmethoxy)-2-(phenylmethoxymethyl)oxan-3-yl]oxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] benzoate
• 化学式: C₆₂H₆₄O₁₂
• 分子量: 1001.18
• InChiKey: YTLQXTIJYNMDGG-AWMNSVLNSA-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：
  0.31
• 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-O-benzoyl-3,4,6-tri-O-benzyl-1-thio-β-D-galactopyranoside 在 calcium sulfate 、 三氟甲磺酸 、 二乙胺基三氟化硫 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 14.0h， 生成 methyl 4-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,3,6-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  A Catalytic and Stereoselective Glycosylation withβ-Glycosyl Fluorides

  摘要：

  A catalytic and stereoselective glycosylation of several glycosyl accepters with beta-D-glycosyl fluoride was successfully performed in the presence of a catalytic amount of trityl tetrakis(pentafluorophenyl)borate (TrB(C6F5)(4)) or trifluoromethanesulfonic acid (TfOH). When TrB(C6F5)(4) was used as a catalyst in the solvent pivalonitrile/(trifluoromethyl)benzene 1:5, the glycosylation proceeded smoothly to afford the glycosides in high yields with high beta-D-stereoselectivities (see Table 3). Further, the glycosylation by the armed-disarmed strategy in the presence of this catalyst was established (see Table 4). Similarly, glycosylation catalyzed by the strong protic acid TfOH afforded the corresponding beta-D-glycosides in good-to-excellent yields on treating beta-D-glycosyl fluorides having a 2-O-benzoyl group with various glycosyl accepters including thioglycosides (see Tables 6 and 7).

  DOI：

  10.1002/1522-2675(20000809)83:8<1901::aid-hlca1901>3.0.co;2-q

文献信息

• A Streamlined Regenerative Glycosylation Reaction: Direct, Acid‐Free Activation of Thioglycosides
  作者：Samira Escopy、Yashapal Singh、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1002/chem.202003479

  日期：2021.1.4

  (HOFox) is able to mediate glycosylations via intermediacy of OFox imidates. Thioglycoside precursors were first converted into the corresponding glycosyl bromides that were then converted into the OFox imidates in the presence of Ag2O followed by the activation with catalytic Lewis acid in a regenerative fashion. Reported herein is a direct conversion of thioglycosides via the regenerative approach

  我们的小组之前曾报道过，3,3-二氟吲哚（HOFox）能够通过 OFox 亚胺酸酯的中介来介导糖基化。硫糖苷前体首先转化为相应的糖基溴化物，然后在 Ag 2 O存在下转化为 OFox 亚胺酸酯，然后以再生方式用催化路易斯酸活化。本文报道了通过再生方法直接转化硫糖苷，该方法绕过了溴化物的中介并消除了对基于重金属的促进剂的需要。在中性反应条件下仅使用 1 当量即可实现硫糖苷的直接再生活化。不含酸性添加剂的 NIS 和催化 HOFox。
• Glycosyl Formates: Glycosylations with Neighboring-Group Participation
  作者：Liang Yang、Christian Marcus Pedersen

  DOI：10.3390/molecules27196244

  日期：——

  model glycosyl acceptors of varied steric bulk and reactivity. Bismuth triflate was the preferred catalyst and KPF6 was used as an additive. The 1,2-trans-selectivities resulting from neighboring-group participation were excellent and the glycosylations were generally high-yielding.

  使用甲酸作为唯一试剂，由相应的原酸酯一步合成受保护的 2-O-苄基化糖基甲酸酯。合成了吡喃葡萄糖基、吡喃甘露糖基和吡喃半乳糖基供体，并使用具有不同空间体积和反应性的模型糖基受体研究了它们的糖基化特性。三氟甲磺酸铋是优选的催化剂，KPF 6用作添加剂。由相邻组参与产生的 1,2-反式选择性非常好，并且糖基化通常是高产的。