3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1-3)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose | 64694-26-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1-3)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
• 英文别名: 1,2:5,6-Di-O-isopropylidene-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-glucofuranose；3-O-1,2:5,6-di-O-isopropylidene-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-glucofuranose；1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-yl 2,3,4,6-tetra-O-benzyl-α-D-galactopyranose；3-O-(tetra-O-benzyl-α-D-galactopyranosyl)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose；(3aR,5R,6S,6aR)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-6-[(2R,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxy-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 64694-26-4
• 化学式: C₄₆H₅₄O₁₁
• 分子量: 782.928
• InChiKey: OIGCVNUVBSVJER-CUVOSQDXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  57
• 可旋转键数：
  16
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-(1-3)-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 palladium on activated charcoal 作用下， 以 乙醇 为溶剂， 反应 12.0h， 以90%的产率得到3-O-α-D-galactopyranosyl-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Application of the imidate procedure to α-d-galactosyltion

  摘要：

  DOI：

  10.1016/s0008-6215(00)81040-x
• 作为产物：
  描述：

  2-pyridyl 2,3,4,6-tetra-O-benzyl-1-thio-D-galactopyranoside 以67%的产率得到
  参考文献：
  名称：

  REDDY, G. VENUGOPAL;KULKARNI, VINAYAK R.;MEREYALA, HARI BABU, TETRAHEDRON LETT., 30,(1989) N2, C. 4283-4286

  摘要：

  DOI：

文献信息

• Stereoselective synthesis of α-linked saccharides by use of per O-benzylated 2-pyridyl 1-thio hexopyranosides as glycosyl donors and methyl iodide as an activator
  作者：Hari Babu Mereyala、G Venugopal Reddy

  DOI：10.1016/s0040-4020(01)86571-6

  日期：1991.8

  D-manno-(3) and L-rhamno-(4) configurations have been efficiently coupled with diverse sugar alcohols (6,8–11) on activation by methyl iodide to obtain the α-linked disaccharides (7,12–19). Coupling of donor 1 with the disaccharide acceptor 20 and the disaccharide donor 5 with 8 to obtain α-linked trisaccharides 21 and 22 is also described. A possible mechanism for the α-selectivity is also discussed

  描述了一种新的，实用的，立体选择性糖苷化方法，其中每个D-葡萄糖-（1），D-半乳糖-（2），D-甘露聚糖-（- ）的O-苄基化2-吡啶基1-硫代-α/β-己吡喃糖基3）和L-鼠李糖（4）构型已通过甲基碘活化与各种糖醇（6,8-11）有效偶联，获得了α-连接的二糖（7,12-19）。供体1与二糖受体20的偶联，以及二糖供体5与8的偶联，以获得α-连接的三糖21和22也进行了描述。还讨论了α选择性的可能机理。
• A mild general method for the synthesis of ∝-linked disaccharides
  作者：G.Venugopal Reddy、Vinayak R. Kulkarni、Hari Babu Mereyala

  DOI：10.1016/s0040-4039(01)80711-5

  日期：1989.1

  Stereoselective ∝-glycosylations may be achieved using stable 2-pyridyl thioglycosides (anomeric mixture) having a non-participating 2-substituent as glycosyl donor and methyl iodide as an activator.

  使用具有非参与性2-取代基作为糖基供体和甲基碘作为活化剂的稳定的2-吡啶基硫代糖苷（端基异构体混合物）可以实现立体选择性的β-糖基化。
• Glycosyl iodides are highly efficient donors under neutral conditions
  作者：Michael J. Hadd、Jacquelyn Gervay

  DOI：10.1016/s0008-6215(99)00146-9

  日期：1999.7

  Abstract Glycosyl iodides have been prepared and subjected to glycosylation under neutral conditions. The reactions are highly efficient, giving α glycosides even with sterically demanding glycosyl acceptors. Glucosyl iodides react with allyl alcohol slowest and require refluxing conditions. Galactosyl iodides are intermediate in reactivity, providing the allyl glycoside in 3 h at room temperature

  摘要制备了糖基碘化物并在中性条件下进行糖基化。该反应是高效的，即使具有空间上要求的糖基受体也能得到α糖苷。葡萄糖基碘与烯丙醇的反应最慢，需要回流条件。半乳糖基碘化物是反应性的中间产物，在室温下3小时内可提供烯丙基糖苷，而岩藻糖基碘化物的糖基化在相似条件下可在不到1小时内发生。用包括异头羟基在内的各种受体证明了反应的范围和局限性，得到了海藻糖类似物。在不存在C-2参与的情况下，只需将溶剂从苯改成乙腈就可以实现葡萄糖基碘化物的β-选择性糖基化。
• [EN] A HIGHLY EFFICIENT GLYCOSYLATION CHEMISTRY ENABLED BY A DIRECTING-GROUP THAT IS PART OF THE ANOMERIC LEAVING-GROUP<br/>[FR] CHIMIE DE GLYCOSYLATION HAUTEMENT EFFICACE ACTIVÉE PAR UN GROUPE DIRECTEUR FAISANT PARTIE DU GROUPE PARTANT ANOMÉRIQUE
  申请人：UNIV CALIFORNIA

  公开号：WO2022165224A1

  公开（公告）日：2022-08-04

  Broadly applicable and stereoselective formation of glycosidic linkage remains challenging yet of critical importance in giycoscience. By developing an SN2 glycosylation, this work advances a general solution to this challenge via stereoinversion at the anomeric position of glycosyl ester donors. This SN2 process is enabled by a basic directing-group in the leaving-group, which is activated by a cationic gold catalyst or any other electrophilic reagent. Unlike all the reported directing group approaches, this strategy is applicable to any glycosyl donors - a long sought-after yet unmet goal in carbohydrate chemistry; moreover, the basic directing-group upon glycosylation is lost as part of the leaving-group and hence traceless in the glycoside products, therefore avoiding potential complications in downstream transformations. Highly selective construction of glycosidic bonds including challenging 1,2-cis glycosidic bonds is achieved in excellent yields. The strategy is applied iteratively to access oligosaccharides and can distinguish alcohols with different steric hindrance.

  广泛适用且立体选择性的糖苷键形成仍然具有挑战性，但在糖科学中至关重要。通过开发SN2糖基化，本研究通过糖酯供体的异构反转在糖基位置上推进了对这一挑战的普遍解决方案。此SN2过程由离去基中的碱性定向基启用，该定向基由阳离子金催化剂或任何其他亲电试剂激活。与所有报道的定向基方法不同，该策略适用于任何糖基供体-这是糖化学中一直追求但未能达成的目标；此外，糖基化后的碱性定向基将作为离去基的一部分而丢失，并且在糖苷产物中没有痕迹，因此避免了下游转化中的潜在复杂性。高度选择性的糖苷键构建，包括具有挑战性的1,2-顺式糖苷键，以极高的收率实现。该策略被迭代应用于访问寡糖，并且可以区分不同立体障碍的醇。
• Glycosyl Disulfides:  Novel Glycosylating Reagents with Flexible Aglycon Alteration
  作者：Elizabeth J. Grayson、Sarah J. Ward、Alison L. Hall、Phillip M. Rendle、David P. Gamblin、Andrei S. Batsanov、Benjamin G. Davis

  DOI：10.1021/jo051374j

  日期：2005.11.1

  Glycosyl disulfides have been shown for the first time to be effective glycosyl donors. Glucosylation and galactosylation of a panel of representative alcohol acceptors allowed the formation of 28simple glycosides, disaccharides, and glycoamino acids in yields of up to 90%. As well as providing a novel class of effective glycosyl donors, the ability to easily alter the nature of the aglycon and the ability to differently activate donors that differ only in their aglycon simply through altering conditions lends glycosyl disulfide donors to their use in latent-active reactivity tuning Strategies,.