1-O-t-butyl-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranose | 380450-60-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-O-t-butyl-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranose
• 英文别名: tert-butyl 2-deoxy-3,4,6-tri-O-benzyl-α-D-galactopyranoside；t-butyl-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranoside；tert-butyl 3,4,6-tri-O-benzyl-α-D-lyxo-hexopyranoside；1-O-t-butyl-3,4,6-tri-O-benzyl-2-deoxy-D-galactopyranose
• CAS: 380450-60-2
• 化学式: C₃₁H₃₈O₅
• 分子量: 490.64
• InChiKey: UTNRVMSOMWNVQP-SKKKGAJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  36.0
• 可旋转键数：
  11.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  1-O-t-butyl-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranose 在 硫酸 、 双氧水 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 1.0h， 生成 2,4,6-tri-O-benzyl-β-D-lyxo-hexopyranosyl hydroperoxide 、 3,4,6-tri-O-benzyl-2-deoxy-α-D-lyxohexopyranosyl hydroperoxide
  参考文献：
  名称：

  Glycosyl hydroperoxides derived from 2-deoxysugars

  摘要：

  Oxidation of 3,4,6-tri-O-benzyl-2-deoxy-D-glucose and D-galactose or their t-butyl glycosides to the corresponding glycosyl hydroperoxides can be performed with hydrogen peroxide in the presence of an acid catalyst. Several reaction conditions and their influence on the effectiveness of the oxidation are discussed. Separation of the alpha - and beta-anomers of the glycosyl hydroperoxides was achieved through mixed peroxide formation by reaction of the hydroperoxide group with 2-methoxypropene and subsequent deprotection. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2010.09.005
• 作为产物：
  描述：

  3,4,6-三邻苄基半乳醛 、 叔丁醇 在 copper(I) bromide 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 以65%的产率得到1-O-t-butyl-3,4,6-tri-O-benzyl-2-deoxy-α-D-galactopyranose
  参考文献：
  名称：

  铜催化立体选择性合成 2-脱氧半乳糖苷

  摘要：

  开发了一种基于 Cu(II) 催化反应合成 2-脱氧-O-半乳糖苷的有效糖基化方法，无需额外配体。糖基化适用于不同的受保护糖基供体和广泛的受体，包括醇、氨基酸、糖和苯酚，并且在温和条件下以优异的收率和高α-选择性进行。该反应在克级规模上很容易进行，其多功能性体现在低聚糖的合成中。

  DOI：

  10.1055/s-0040-1707098

文献信息

• Fluorine-Directed β-Galactosylation: Chemical Glycosylation Development by Molecular Editing
  作者：Estelle Durantie、Christoph Bucher、Ryan Gilmour

  DOI：10.1002/chem.201200468

  日期：2012.6.25

  Validation of the 2‐fluoro substituent as an inert steering group to control chemical glycosylation is presented. A molecular editing study has revealed that the exceptional levels of diastereocontrol in glycosylation processes by using 2‐fluoro‐3,4,6‐tri‐O‐benzyl glucopyranosyl trichloroacetimidate (TCA) scaffolds are a consequence of the 2R,3S,4S stereotriad. This study has also revealed that epimerization

  提出了将2-氟取代基作为控制化学糖基化反应的惰性指导基团的验证方法。一项分子编辑研究表明，通过使用2-氟-3,4,6-三-O-苄基吡喃葡萄糖基三氯乙酰亚氨酸酯（TCA）支架，糖基化过程中非对映异构控制的异常水平是2 R，3 S，4的结果S立体三合会。这项研究还表明，C4的差向异构作用会导致β选择性大大提高（高达β/α300：1）。
• Organocatalytic Glycosylation by Using Electron-Deficient Pyridinium Salts
  作者：Somnath Das、Daniel Pekel、Jörg-M. Neudörfl、Albrecht Berkessel

  DOI：10.1002/anie.201503156

  日期：2015.10.12

  A new organocatalytic glycosylation method based on electron‐deficient pyridinium salts is reported. At ambient temperature and catalyst loadings as low as 1 mol %, 2‐deoxyglycosides were formed from benzyl‐ and silyl‐protected glycals and primary or secondary glycosyl acceptors, with excellent yields and anomeric selectivity. Mechanistic investigations point to alcohol–pyridinium conjugates (1,2‐addition

  报道了一种新的基于缺电子吡啶鎓盐的有机催化糖基化方法。在环境温度和低至1 mol％的催化剂负载量下，由苄基和甲硅烷基保护的糖基和伯或仲糖基受体形成2-脱氧糖苷，具有优异的收率和端基异构体选择性。机理研究表明，醇-吡啶共轭物（1,2-加成产物）是催化循环中的关键中间体。
• Stereoselective Electro‐2‐deoxyglycosylation from Glycals
  作者：Miao Liu、Kai‐Meng Liu、De‐Cai Xiong、Hanyu Zhang、Tian Li、Bohan Li、Xianjin Qin、Jinhe Bai、Xin‐Shan Ye

  DOI：10.1002/anie.202006115

  日期：2020.8.24

  report a novel and highly stereoselective electro‐2‐deoxyglycosylation from glycals. This method features excellent stereoselectivity, scope, and functional‐group tolerance. This process can also be applied to the modification of a wide range of natural products and drugs. Furthermore, a scalable synthesis of glycosylated podophyllotoxin and a one‐pot trisaccharide synthesis through iterative electroglycosylations

  我们报道了一种来自糖基的新型且高度立体选择性的电-2-脱氧糖基化反应。该方法具有出色的立体选择性，范围和功能组公差。该方法也可以用于多种天然产物和药物的改性。此外，还实现了糖基鬼臼毒素的可扩展合成和通过迭代电糖基化的单锅三糖合成。
• Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis
  作者：Yuya Nakatsuji、Yusuke Kobayashi、Yoshiji Takemoto

  DOI：10.1002/anie.201907129

  日期：2019.10

  The direct 2-deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2-deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2-deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2-deoxyglycosylation of amide groups using a newly designed

  亲核试剂与糖的直接2-脱氧糖基化会导致生物学上和药理上重要的2-deoxysugar化合物。尽管已经很好地开发了羟基和磺酰胺基团的直接加成，但是迄今为止尚未报道酰胺基团的直接2-脱氧糖基化。在这里，我们显示了使用新设计的布朗斯台德酸催化剂在温和条件下的酰胺基团的直接直接2-脱氧糖基化。通过机理研究，我们发现酰胺基团可以抑制酸催化剂，并且该抑制作用使得2-脱氧糖基化反应变得困难。扩散排序的二维NMR光谱分析表明，与其他酸催化剂相比，2-氯偶氮盐催化剂不太可能与酰胺形成聚集体。氯原子和催化剂的扩展π骨架对这一现象起着至关重要的作用。酰胺抑制作用的这种相对不敏感性比酸度的强度更负责催化活性。
• The synthesis of 2-deoxy-α-d-glycosides from d-glycals catalyzed by TMSI and PPh3
  作者：Xi-Kai Cui、Ming Zhong、Xiang-Bao Meng、Zhong-Jun Li

  DOI：10.1016/j.carres.2012.06.004

  日期：2012.9

  2-Deoxyglycosides were synthesized in high alpha-selectivity by the direct addition of alcohols to D-glucal and D-galactal catalyzed by TMSI and PPh3. The acid labile isopropylidene group is tolerated under this condition. (C) 2012 Elsevier Ltd. All rights reserved.