2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl trichloroacetimidate | 226211-26-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl trichloroacetimidate
• 英文别名: Bz(-2)[Bz(-3)][Bz(-5)][Bz(-6)]Galf(b)-O-C(NH)CCl3；[(2R)-2-benzoyloxy-2-[(2S,3S,4R,5S)-3,4-dibenzoyloxy-5-(2,2,2-trichloroethanimidoyl)oxyoxolan-2-yl]ethyl] benzoate
• CAS: 226211-26-3
• 化学式: C₃₆H₂₈Cl₃NO₁₀
• 分子量: 740.978
• InChiKey: VDEJMCCMUXHBRI-NFUQQPFBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  50
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  148
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl trichloroacetimidate 在 三氟甲磺酸三甲基硅酯 吡啶 、 MS 4 Angstroem 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 9.0h， 生成 2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl-(1->3)-5,6-di-O-acetyl-1,2-O-isopropylidene-α-D-galactopyranose
  参考文献：
  名称：

  First synthesis of β-d-Galf-(1→3)-d-Galp—the repeating unit of the backbone structure of the O-antigenic polysaccharide present in the lipopolysaccharide (LPS) of the genus Klebsiella

  摘要：

  b-D-Galactofuranosyl-(1 --> 3)-D-galactopyranose (1), the repeating unit of the backbone structure of the O-antigenic polysaccharide present in the lipopolysaccharide (LPS) of the genus Klebsiella, has been efficiently synthesized using 1,2:5,6-di-O-isopropylidine-alpha-D-galactofuranose (3) as the glycosyl acceptor and 2,3,5,6-tetra-0-benzoyl-p-D-galactofuranosyl trichloroacetimidate (6) as the glycosyl donor with TMSOTf as catalyst by the well-known Schmidt glycosylation method. The preparation of 3 was improved by increasing the ratio of DMF to acetone and employing a solid-supported catalyst. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(03)00076-4
• 作为产物：
  描述：

  [(2R)-2-benzoyloxy-2-[(2S,3S,4R)-3,4-dibenzoyloxy-5-bromooxolan-2-yl]ethyl] benzoate 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 1.17h， 生成 2,3,5,6-tetra-O-benzoyl-β-D-galactofuranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of β-d-Galf-(1−3)-d-GlcNAc by the Trichloroacetamidate Method and of β-d-Galf-(1−6)-d-GlcNAc by SnCl₄-Promoted Glycosylation

  摘要：

  In a continuation of our studies on the characterization of the glycoproteins of T. cruzi new galactofuranosyl disaccharides were synthesized. beta-D-Galf-(1-3)-D-GlcNAc (1) was prepared by employing the trichloroacetamidate procedure for the glycosylation step, The mild conditions of this reaction are appropriate for condensation of 2,3,5,6-tetra-O-benzoyl-beta-D-galactofuranosyl trichloroacetamidate (6) with acid-labile benzyl 2-acetamido-4,6-O-benzylidene-2-deoxy-alpha-D-glucopyranoside (3). On the other hand, tin(IV) chloride promoted condensation of benzyl 2-acetamido-3-O-benzoyl-2-deoxy-alpha-D-glucopyranoside (11) with penta-O-benzoyl-alpha,beta-D-galactofuranose (4) gave the derivative of beta-D-Galf-(1-6)-D-GlcNAc (2) in 78% yield.

  DOI：

  10.1021/ol9905811

文献信息

• Synthesis of Branched Dithiotrisaccharides via Ring-Opening Reaction of Sugar Thiiranes
  作者：Evangelina Repetto、Verónica E. Manzano、María Laura Uhrig、Oscar Varela

  DOI：10.1021/jo2018685

  日期：2012.1.6

  (3→3)-disulfide 19, which resulted from the oxidative dimerization of 17. However, the S-acetyl derivative of 17 could be obtained in good yield (62%) by LiAlH4 reduction of the crude mixture 17–19, followed by acetylation. The same sequence of reactions starting from 14 and the 1-thiolate of Galp afforded the per-O,S-acetyl derivative of Galp-β-S-(1→4)-3,4-dithio-α-d-Glcp-O-iPr (23), which was selectively

  描述了从各自的六呋喃糖或六吡喃糖环氧前体合成5，6-和3，4-噻喃衍生物的令人满意的程序。通过1-thioaldoses硫杂丙环的受控开环反应物成功地完成，得到选择性，区域选择性和立体选择性，β-小号- （1→4）-3,4- dithiodisaccharides。例如，过-O-乙酰基-1-硫代葡萄糖（16）对2-丙基2,6-二-O-乙酰基-3,4-表硫基-α- d-吡喃半乳糖苷的C-4的区域选择性攻击（14）），得到衍生物GLC的p -β-小号- （1→4）-3,4- dithioGlc p - ø -我PR（17）。该硫二糖伴有在16和17之间形成的（1→3）-二硫化物18和对称的（3→3）-二硫化物19，这是由于17的氧化二聚作用而引起的。然而，小号-乙酰基衍生物的17可以以良好的收率（62％）的LiAlH通过获得4还原粗混合物的17 - 19，接着乙酰化。从开始反应的相同序列14和Gal的1
• Synthesis of the O-linked hexasaccharide containing β-d-Galf-(1→2)-β-d-Galf in Trypanosoma cruzi mucins
  作者：Gustavo A. Kashiwagi、Verónica M. Mendoza、Rosa M. de Lederkremer、Carola Gallo-Rodriguez

  DOI：10.1039/c2ob25741f

  日期：——

  hexasaccharide β-D-Galp-(1→2)-[β-D-Galp-(1→3)]-β-D-Galp-(1→6)-[β-D-Galf(1→2)-β-D-Galf(1→4)]-D-GlcNAc (1) is the largest carbohydrate structure released as alditol by reductive β-elimination from mucins of some strains of T. cruzi. The terminal β-D-Galp units are sites of sialylation by trans-sialidase which transfers sialic acid from the host to the parasite. Hexasaccharide 1 was synthesized by a [3 + 3]-convergent

  六糖β- D -Gal p-（1→2）-[β- D -Gal p-（1→3）]-β- D -Gal p-（1→6）-[β- D -Gal f（1→2）-β- d -Gal ˚F（1→4）] - d -GlcNAc（1）是从一些菌株的粘蛋白释放作为醛糖醇通过还原性β-消除最大碳水化合物结构锥虫。末端β- D- Gal p单位是通过反唾液酸酶进行唾液酸化的位点，其将唾液酸从宿主转移至寄生虫。六糖1通过基于腈辅助糖基化的[3 + 3]聚合策略，使用三氯乙酰亚氨酸酯方法合成了SnO。所述β- d -Gal ˚F - （1→2）-β- d -Gal ˚F - d -GlcNAc合成子依次从还原端构造成的非还原端使用苄α- d -galactofuranoside作为起始原料内部Gal f单元。对这种新型前体的选择是在一个反应​​步骤中从半乳糖中获得的，从而可以在O-2处引入一个正交的参与的乙酰丙酰基。因此，Gal
• Experimental and theoretical study of the O3/O4 regioselectivity of glycosylation reactions of glucopyranosyl acceptors
  作者：Enrique A. Del Vigo、Carlos A. Stortz、Carla Marino

  DOI：10.1016/j.tet.2020.131719

  日期：2020.12

  The knowledge of the regioselectivity between different hydroxyl groups of glycosyl acceptors is valuable in planning simple strategies for the synthesis of oligosaccharides, minimizing the use of protecting groups. With the aim of obtaining deeper knowledge on this subject, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,6-di-O-protected methyl α- and β-glucopyranosides in glycosylation

  糖基受体的不同羟基之间的区域选择性的知识对于规划寡糖合成的简单策略，最大限度地减少保护基的使用非常有价值。为了获得对该主题的更深入的了解，我们分析了2,6-di- O的OH-3和OH-4基团的相对反应性糖基化反应中保护的甲基α-和β-吡喃葡萄糖苷。通过简单的程序制备糖基受体，并将半乳糖-吡喃糖基和呋喃糖基三氯乙酰亚氨酸酯评估为糖基供体。将实验结果与通过分子建模方法获得的结果进行对比。分子模型和实验结果基本吻合。已经表明，通过选择正确的端基异构体和保护基团，可以使用适当的葡糖基受体选择性地安装1→3或1→4键。
• Regioselectivity of glycosylation reactions of galactose acceptors: an experimental and theoretical study
  作者：Enrique A Del Vigo、Carlos A Stortz、Carla Marino

  DOI：10.3762/bjoc.15.294

  日期：——

  Regioselective glycosylations allow planning simpler strategies for the synthesis of oligosaccharides, and thus reducing the need of using protecting groups. With the idea of gaining further understanding of such regioselectivity, we analyzed the relative reactivity of the OH-3 and OH-4 groups of 2,6-diprotected methyl α- and β-galactopyranoside derivatives in glycosylation reactions. The glycosyl acceptors

  区域选择性糖基化允许为寡糖的合成规划更简单的策略，从而减少了使用保护基的需要。为了进一步了解这种区域选择性，我们分析了糖基化反应中2，6-二保护的甲基α-和β-吡喃半乳糖苷衍生物的OH-3和OH-4基团的相对反应性。通过简单的方法有效地制备了糖基受体，并评估了具有不同反应性的糖基供体。由于OH-3基团的赤道取向，实现了对1→3产物的高区域选择性。分子建模方法支持了支持O-3取代的总体趋势，尽管它显示出一些无法解释控制某些受体之间区域选择性差异的微妙因素的能力。然而，可以通过使用本文测定的一些受体在区域上选择性地安装Galp-（β1→3）-Galp连接。
• Synthesis of oligosaccharides related to galactomannans from<i>Aspergillus fumigatus</i>and their NMR spectral data
  作者：V. B. Krylov、D. A. Argunov、A. S. Solovev、M. I. Petruk、A. G. Gerbst、A. S. Dmitrenok、A. S. Shashkov、J.-P. Latgé、N. E. Nifantiev

  DOI：10.1039/c7ob02734f

  日期：——

  full assignment of 1H and 13C signals and the determination of 13C NMR glycosylation effects. The obtained NMR database on 13C NMR chemical shifts for oligosaccharides representing galactomannan fragments forms the basis for further structural analysis of galactomannan related polysaccharides by a non-destructive approach based on the calculation of the 13C NMR spectra of polysaccharides by additive

  相关的危险的真菌病原体的抗原性半乳甘露聚糖模型的寡糖的合成烟曲霉已经执行使用pyranoside-成-furanoside（PIF）重排和控制O（5）→O（6）苯甲酰基迁移作为键的合成方法。通过NMR光谱研究了所制备的化合物以及一些先前合成的寡糖，并完整分配了1 H和13 C信号，并确定了13 C NMR糖基化作用。在13上获得的NMR数据库代表半乳甘露聚糖片段的寡糖的C NMR化学位移为通过加成方案计算多糖的13 C NMR谱的非破坏性方法，为半乳甘露聚糖相关多糖的进一步结构分析奠定了基础。