ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranoside | 152964-76-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranoside
• 英文别名: [(2R,3S,4S,5R,6S)-6-ethylsulfanyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]methanol
• CAS: 152964-76-6
• 化学式: C₂₉H₃₄O₅S
• 分子量: 494.652
• InChiKey: AZQPSLVUJGSMNT-LLQHYSMESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  35
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranoside 在 4 A molecular sieve 、 四乙基溴化铵 、 DMTST 作用下， 以 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 53.0h， 生成 2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl-(1->6)-2,3,4-tri-O-benzyl-α-D-galactopyranosyl-(1->3)-1,2,5,6-tetra-O-acetyl-α,β-D-galactofuranose
  参考文献：
  名称：

  Synthesis of the Leishmania LPG Core Heptasaccharyl myo-Inositol

  摘要：

  Total synthesis of the core heptasaccharyl myo-inositol, Galp(alpha1-6)Galp(alpha1-3)Galf(beta1-3)[Glcp(alpha1-PO4-6)Manp](alpha1-3)Manp(alpha1-4)GlcNp(alpha1-6)Ins-1-PO4, and the corresponding hexasaccharyl myo-inositol, Galp(alpha1-6)Galp(alpha1-3)Galf(beta1-3)Manp(alpha1-3)Manp(alpha1-4)GlcNp(alpha1-6)Ins-1-PO4, found in the lipophosphoglycans of Leishmania parasites are described. The target molecules contain synthetic challenges such as an unusual internal galactofuranosyl residue and an anomeric phosphodiester. The synthesis was accomplished using a convergent block synthetic strategy. Four building blocks, a trigalactoside, a dimannoside, a glucosyl inositolphosphate, and a glucosyl-alpha -1-H-phosphonate, all appropriately protected, were used. The trigalactoside was linked to the dimannoside followed by glycosylation with the glucosyl inositolphosphate to produce the fully protected hexasaccharyl myo-inositol. Subsequent oxidative coupling of the glucosyl-H-phosphonate formed the anomeric phosphodiester linkage to produce the protected heptasaccharyl myo-inositol. Both the assembly order of the subunits and sequence of deprotection were essential for the successful synthesis of these complex molecules. The deprotection was accomplished by deacetylation and clevage of benzyl ethers with sodium in liquid ammonia, followed by acidic deacetalization/desilylation to produce the target molecules.

  DOI：

  10.1021/ja001515t
• 作为产物：
  描述：

  1-硫代-Β-D-乙基半乳糖苷 在 吡啶 、 4-二甲氨基吡啶 、 sodium hydride 、 对甲苯磺酸 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.0h， 生成 ethyl 2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis of the Leishmania LPG Core Heptasaccharyl myo-Inositol

  摘要：

  Total synthesis of the core heptasaccharyl myo-inositol, Galp(alpha1-6)Galp(alpha1-3)Galf(beta1-3)[Glcp(alpha1-PO4-6)Manp](alpha1-3)Manp(alpha1-4)GlcNp(alpha1-6)Ins-1-PO4, and the corresponding hexasaccharyl myo-inositol, Galp(alpha1-6)Galp(alpha1-3)Galf(beta1-3)Manp(alpha1-3)Manp(alpha1-4)GlcNp(alpha1-6)Ins-1-PO4, found in the lipophosphoglycans of Leishmania parasites are described. The target molecules contain synthetic challenges such as an unusual internal galactofuranosyl residue and an anomeric phosphodiester. The synthesis was accomplished using a convergent block synthetic strategy. Four building blocks, a trigalactoside, a dimannoside, a glucosyl inositolphosphate, and a glucosyl-alpha -1-H-phosphonate, all appropriately protected, were used. The trigalactoside was linked to the dimannoside followed by glycosylation with the glucosyl inositolphosphate to produce the fully protected hexasaccharyl myo-inositol. Subsequent oxidative coupling of the glucosyl-H-phosphonate formed the anomeric phosphodiester linkage to produce the protected heptasaccharyl myo-inositol. Both the assembly order of the subunits and sequence of deprotection were essential for the successful synthesis of these complex molecules. The deprotection was accomplished by deacetylation and clevage of benzyl ethers with sodium in liquid ammonia, followed by acidic deacetalization/desilylation to produce the target molecules.

  DOI：

  10.1021/ja001515t

文献信息

• Stereocontrolled α-Galactosylation under Cooperative Catalysis
  作者：Melanie Shadrick、Yashapal Singh、Alexei V. Demchenko

  DOI：10.1021/acs.joc.0c01279

  日期：2020.12.18

  A recent discovery of a cooperative catalysis comprising a silver salt and an acid led to a dramatic improvement in the way glycosyl halides are glycosidated. Excellent yields have been achieved, but the stereoselectivity achieved with 2-O-benzylated donors was poor. Reported herein is our first attempt to refine the stereoselectivity of the cooperatively catalyzed galactosylation reaction. Careful

  最近发现的包含银盐和酸的协同催化导致糖基卤化物糖苷化方式的显着改进。已经实现了极好的产率，但是用 2- O-苄基化供体实现的立体选择性很差。本文报道的是我们首次尝试改进协同催化的半乳糖基化反应的立体选择性。仔细优化反应条件以及研究远程保护基团的作用，对具有不同保护的半乳糖基供体的各种糖基受体的 α-半乳糖基化进行了出色的立体控制。
• The parallel synthesis of a disaccharide library using a solid phase, peptide-templated strategy
  作者：Jessica Burt、Tony Dean、Stuart Warriner

  DOI：10.1039/b313571c

  日期：——

  A novel strategy for the synthesis of oligosaccharides, involving the use of a solid phase peptide template, has been successfully applied to the construction of a twelve member disaccharide library.

  一种新的寡糖合成策略，使用固相肽模板，已经成功应用于构建一个十二个成员的二糖库。
• Regio- and chemoselective reductive cleavage of 4,6-O-benzylidene-type acetals of hexopyranosides using BH3·THF–TMSOTf
  作者：Katalin Daragics、Péter Fügedi

  DOI：10.1016/j.tetlet.2009.03.194

  日期：2009.6

  cyclic acetals of carbohydrates undergo efficient reductive ring opening using BH3·THF and a catalytic amount of TMSOTf at room temperature. 4,6-O-Benzylidene-hexopyranosides afford the corresponding 4-O-benzyl ethers exclusively, in high yields. Other benzylidene-type acetals, such as naphthylmethylene and 4-methoxybenzylidene acetals are also cleaved with the same reagent. The conversions are highly regio-

  碳水化合物的亚苄基型环状缩醛在室温下使用BH 3 ·THF和催化量的TMSOTf进行有效的还原性开环。4,6- ø -亚苄基- hexopyranosides得到相应的4- ø -苄基醚排他地，以高收率。其他亚苄基型缩醛，例如萘基亚甲基和4-甲氧基亚苄基缩醛也可以用相同的试剂裂解。该转化具有高度的区域选择性和立体选择性，并以优异的产率提供了苄基型醚。
• Synthesis of inositol phosphoglycans containing thiol-terminated spacers for efficient coupling to maleimide functionalized solid phases or proteins
  作者：Jan Lindberg、Peter Strålfors、Peter Konradsson

  DOI：10.1016/s0040-4020(02)00359-9

  日期：2002.5

  The synthesis of inositol phosphoglycans (IPGs), analogous to second messengers of insulin, to provide a small targeted library of compounds is described. These derivatives contain the glucosamine(α1–6)myo-inositol 1,2-cyclic phosphate motif. A thiol-terminated spacer was introduced, for their immobilization, by a radical elongation of an allyl ether with benzyl mercaptane.

  描述了类似于胰岛素的第二信使的肌醇磷酸聚糖（IPG）的合成，以提供小的目标化合物库。这些衍生物含有葡糖胺（α1-6）肌醇肌醇-1,2-环磷酸基序。通过烯丙基醚与苄基硫醇的自由基伸长，引入了巯基封端的间隔基，以使其固定。
• The Influence of the Electron Density in Acyl Protecting Groups on the Selectivity of Galactose Formation
  作者：Kim Greis、Sabrina Leichnitz、Carla Kirschbaum、Chun-Wei Chang、Mei-Huei Lin、Gerard Meijer、Gert von Helden、Peter H. Seeberger、Kevin Pagel

  DOI：10.1021/jacs.2c05859

  日期：2022.11.9

  Cryogenic infrared spectroscopy in helium nanodroplets and density functional theory calculations revealed the existence of dioxolenium-type intermediates for this reaction, which suggests that remote participation of the pivaloyl protecting group is the origin of the high α-selectivity of the pivaloylated building blocks. According to these findings, an α-selective galactose building block for glycosynthesis

  1,2-顺式的立体选择性形成-糖苷键是碳水化合物合成的主要瓶颈。我们在这里通过微调远程参与的效率来研究酰基保护基团中的电子密度如何影响立体选择性。富电子 C4-新戊酰化半乳糖结构单元显示出前所未有的 α-选择性。另一方面，具有吸电子基团的三氟乙酰化对应物表现出较低的选择性。氦纳米液滴中的低温红外光谱和密度泛函理论计算揭示了该反应中存在二氧杂烯鎓型中间体，这表明新戊酰保护基的远程参与是新戊酰化结构单元高 α-选择性的来源。根据这些发现，基于合理的考虑开发了一种用于糖合成的 α-选择性半乳糖构建块，随后用于自动聚糖组装，表现出完全的立体选择性。基于在糖基化反应中获得的选择性以及红外光谱和密度泛函理论的结果，我们提出了这些反应可以进行的机制。