phenyl 2-deoxy-3-O-(4-methoxybenzyl)-1-thio-α-L-fucopyranoside | 167012-22-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: phenyl 2-deoxy-3-O-(4-methoxybenzyl)-1-thio-α-L-fucopyranoside
• 英文别名: (2S,3R,4S,6S)-4-[(4-methoxyphenyl)methoxy]-2-methyl-6-phenylsulfanyloxan-3-ol
• CAS: 167012-22-8
• 化学式: C₂₀H₂₄O₄S
• 分子量: 360.474
• InChiKey: PUXDCLQMNGREIX-DILOTOHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  73.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  phenyl 2-deoxy-3-O-(4-methoxybenzyl)-1-thio-α-L-fucopyranoside 在 吡啶 、 sodium hydride 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 mineral oil 为溶剂， 反应 24.67h， 生成
  参考文献：
  名称：

  Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric O-Alkylation with Secondary Electrophiles

  摘要：

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.

  DOI：

  10.1021/ja4116956
• 作为产物：
  描述：

  L-fucal 在 ReOCl₃(SMe₂)(OPPh₃) 、 二正丁基氧化锡 作用下， 以 甲苯 为溶剂， 反应 3.0h， 生成 phenyl 2-deoxy-3-O-(4-methoxybenzyl)-1-thio-α-L-fucopyranoside
  参考文献：
  名称：

  Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric O-Alkylation with Secondary Electrophiles

  摘要：

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.

  DOI：

  10.1021/ja4116956

文献信息

• Glycosylation method
  申请人：The Trustees of Princeton University

  公开号：US06388059B1

  公开（公告）日：2002-05-14

  A method for forming a glycosidic linkage by: (a) contacting a glycoside bearing an anomeric sulfoxide group with a compound bearing a free hydroxyl group in the presence of an organic acid anhydride and a scavenger of sulfenyl esters; and (b) allowing a glycosylation reaction to proceed under conditions effective to produce the glycosidic linkage. In a preferred embodiment of the invention, the glycoside bearing an anomeric sulfoxide group is added to a mixture of the other reactants. In another preferred embodiment of the invention, a Lewis acid is also present in the reaction mixture. This invention is further directed to a method for forming a glycosidic linkage by: (a) forming a solution comprising: a compound bearing a free hydroxyl group, and an organic acid anhydride; (b) adding to the solution a glycoside bearing an anomeric sulfoxide group; and (c) allowing a glycosylation reaction to proceed under conditions effective to produce the glycosidic linkage. In a preferred embodiment of the invention, a Lewis acid is present in the solution.

  通过以下方法形成糖苷键：(a) 在有机酸酐和硫醚酯清除剂存在下，将带有顶夫氧化物基团的糖苷与带有自由羟基团的化合物接触；和(b) 在有效条件下使糖基化反应进行，以产生糖苷键。在本发明的一种首选实施方式中，带有顶夫氧化物基团的糖苷被添加到其他反应物的混合物中。在本发明的另一种首选实施方式中，反应混合物中还存在一种路易斯酸。本发明还涉及通过以下方法形成糖苷键：(a) 形成包括：带有自由羟基团的化合物和有机酸酐的溶液；(b) 向溶液中添加带有顶夫氧化物基团的糖苷；和(c) 在有效条件下使糖基化反应进行，以产生糖苷键。在本发明的一种首选实施方式中，溶液中存在一种路易斯酸。
• Synthesis of 2-Deoxyglycosides Bearing Free Hydroxyl Substituents on the Glycosyl Donor
  作者：Kevin M. Hoang、Xiaoying Zheng、Seth B. Herzon

  DOI：10.1021/acs.joc.2c01003

  日期：2022.8.19

  substituents. The reaction proceeds via prior deprotonation of one or more free hydroxyl groups on a thiophenylglycoside donor, reductive lithiation to generate an anomeric anion intermediate, and addition of this anion to an alkyl 2-(2-methyltetrahydropyranyl) peroxide. By this approach, α-linked glycosides were obtained in 39–84% yields and with >50:1 α/β selectivities. In many instances, β-linked products

  最近在碳水化合物化学领域的努力集中在从带有多个羟基取代基的受体衍生的O-糖苷的位点和立体控制合成上。相比之下，在供体试剂上选择性合成带有游离羟基取代基的O-糖苷的例子很少。在这里，我们报告了 umpolung 糖基化策略在O合成中的应用-衍生自带有游离羟基取代基的供体的糖苷。该反应通过预先对苯硫基糖苷供体上的一个或多个游离羟基进行去质子化、还原锂化以产生异头阴离子中间体并将该阴离子添加到烷基2-(2-甲基四氢吡喃)过氧化物中而进行。通过这种方法，以 39-84% 的产率获得了 α-连接的糖苷，并且具有 >50:1 的 α/β 选择性。在许多情况下，β-连接的产物可以通过异头阴离子中间体的热平衡获得（选择性 = 3.8–8:1 β/α；产率 = 33–68%）。该策略适用于带有最多三个游离羟基的多羟基供体、N-酰化碳水化合物和寡糖的单瓶合成。
• US6388059B1
  申请人：——

  公开号：US6388059B1

  公开（公告）日：2002-05-14
• Direct Synthesis of 2-Deoxy-β-Glycosides via Anomeric <i>O</i>-Alkylation with Secondary Electrophiles
  作者：Danyang Zhu、Kedar N. Baryal、Surya Adhikari、Jianglong Zhu

  DOI：10.1021/ja4116956

  日期：2014.2.26

  An approach for direct synthesis of biologically significant 2-deoxy-beta-glycosides has been developed via O-alkylation of a variety of 2-deoxy-sugar-derived anomeric alkoxides using challenging secondary triflates as electrophiles. It was found a free hydroxyl group at C3 of the 2-deoxy-sugar-derived lactols is required in order to achieve synthetically efficient yields. This method has also been applied to the convergent synthesis of a 2-deoxy-beta-tetrasaccharide.