methyl 3-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,4,6-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 3-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,4,6-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: Bz(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Gal(b1-3)[Bn(-2)][Bn(-4)][Bn(-6)]a-Glc1Me；[(2S,3R,4S,5S,6R)-2-[(2S,3R,4S,5R,6R)-2-methoxy-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-4-yl]oxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] benzoate
• 化学式: C₆₂H₆₄O₁₂
• 分子量: 1001.18
• InChiKey: BDZXSZMZNDNJQP-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 11.0h， 生成 methyl 3-O-(2-O-benzoyl-3,4,6-tri-O-benzyl-β-D-galactopyranosyl)-2,4,6-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

• Palladium(<scp>ii</scp>)-assisted activation of thioglycosides
  作者：Samira Escopy、Yashapal Singh、Alexei V. Demchenko

  DOI：10.1039/d1ob00004g

  日期：——

  Described herein is the first example of glycosidation of thioglycosides in the presence of palladium(II) bromide. While the activation with PdBr2 alone was proven feasible, higher yields and cleaner reactions were achieved when these glycosylations were performed in the presence of propargyl bromide as an additive. Preliminary mechanistic studies suggest that propargyl bromide assists the reaction

  本文描述的是在溴化钯( II )存在下硫代糖苷的糖苷化的第一个实例。虽然单独使用 PdBr 2进行活化已被证明是可行的，但当这些糖基化在炔丙基溴作为添加剂存在的情况下进行时，可以实现更高的产率和更清洁的反应。初步机理研究表明，炔丙基溴通过产生电离络合物来促进反应，从而加速离去基团的离开。研究了与不同糖基受体反应的各种硫代糖苷供体，以确定这种新反应的初始范围。还探索了硫代糖苷相对于其他离去基团的选择性和化学选择性激活。
• 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。
• A Catalytic and Stereoselective Glycosylation withβ-Glycosyl Fluorides
  作者：Teruaki Mukaiyama、Kazuya Takeuchi、Hideki Jona、Hisashi Maeshima、Terunobu Saitoh

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

  日期：2000.8.9

  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).