[(2R,3S,4S,5R,6R)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-methoxyoxan-2-yl]methyl 4-bromobenzoate | 78950-20-6

• 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: [(2R,3S,4S,5R,6R)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-methoxyoxan-2-yl]methyl 4-bromobenzoate
• CAS: 78950-20-6；78950-21-7；78950-22-8；78950-23-9；78950-24-0；136292-83-6
• 化学式: C₃₅H₂₆Br₄O₁₀
• 分子量: 926.201
• InChiKey: JYESNPYPYZSTLC-XFUYZNCPSA-N

物化性质

• 沸点：
  857.0±65.0 °C(Predicted)
• 密度：
  1.83±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.1
• 重原子数：
  49
• 可旋转键数：
  14
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4S,5R,6R)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-methoxyoxan-2-yl]methyl 4-bromobenzoate 在 三氯化铁 作用下， 以 二氯甲烷 为溶剂， 以64%的产率得到methyl 2,3,4,6-tetrakis-O-(p-bromobenzoyl)-α-D-galactopyranoside
  参考文献：
  名称：

  Alkyl Galactopyranosides:  Rotational Population Dependence of the Hydroxymethyl Group on the Aglycon and Its Absolute Configuration and on the Anomeric Configuration

  摘要：

  The rotational populations of the hydroxymethyl group in chiral and nonchiral alkyl alpha- and beta-galactopyranosides proved, on the basis of circular dichroism (CD) and H-1 NMR data, to be dependent on the structure of the aglycon: the population of the gt and tg rotamers increased and decreased, respectively, as the pK(a) of the bonded alcohol (aglycon) increased, while the population of the gg rotamer remained practically constant. Furthermore, low-temperature CD measurements proved that the most stable rotamer is the gt, and not the tg. In addition, a clear correlation between the rotational populations and the absolute configuration of the chiral aglycon was observed; namely, higher and smaller gt and tg populations were observed for the (S)-alkyl beta-D-galactopyranosides than for their (R)-alkyl beta-D-galactopyranoside counterparts, the opposite behavior being observed for the cl-anomers. The results point to the exo anomeric effect as being responsible for these rotational dependencies, as well as to nonbonding interactions between the aglycon and the chromophore at C6 for those stereoisomers having in their aglycon a bulky substituent syn to the endocyclic oxygen (O5). In addition, the chemical shift differences (Delta delta) of the aglyconic protons of galactosylated chiral alcohols proved to be characteristic of the absolute configuration of the bonded chiral alcohol.

  DOI：

  10.1021/jo981002t
• 作为产物：
  描述：

  D-吡喃葡萄糖 在 盐酸 、 4-二甲氨基吡啶 作用下， 以 吡啶 为溶剂， 反应 16.0h， 生成 [(2R,3S,4S,5R,6R)-3,4,5-tris[(4-bromobenzoyl)oxy]-6-methoxyoxan-2-yl]methyl 4-bromobenzoate
  参考文献：
  名称：

  皮克至纳克级的甲基糖苷表征

  摘要：

  摘要我们描述了一种通用的方法，该方法可以表征100 pg至1 ng量的糖。因此，将寡糖进行甲醇分解，然后进行对-溴苯甲酰化或萘甲酰化，并通过高压液相色谱法分离甲基糖苷过酸酯。该方法也适用于氨基糖和乙酰氨基糖。如果需要，可以通过溴苯甲酸酯的特征准M +峰和激子分裂的圆二色性（cd）曲线的极值明确标识分离的糖衍生物。此外，由于聚苯甲酸酯的cd极值可从组分二苯甲酸酯单元的极值中预测出来，因此cd数据可得出有关吡喃葡萄糖的-OH，-NH 2和-NHAc基团未知空间分布的信息。该方法的应用已通过绿色戊糖C进行了证明，

  DOI：

  10.1016/0008-6215(83)88042-2

文献信息

• A CD-Spectroscopic Alternative to Methylation Analysis of Oligosaccharides: Reference Spectra for Identification of Chromophoric Glycopyranoside Derivatives
  作者：William T. Wiesler、Nikolina Berova、Makoto Ojika、Harold V. Meyers、Mayland Chang、Peng Zhou、Lee-Chiang Lo、Masatake Niwa、Reiji Takeda、Koji Nakanishi

  DOI：10.1002/hlca.19900730302

  日期：1990.5.2

  conversion of oligosaccharides to monosaccharide subunits bearing 4-bromobenzoate and 4-methoxycinnamate chromophores have been developed based on acetolysis/bromination reactions for glycosidic cleavage of per (bromobenzoylated) oligosaccharides. The method offers an alternative means to conventional methylation analysis of oligosaccharides.

  提出了一种用于鉴定寡糖中单糖单元及其键合的微型方法。糖成分通过发色降解产物的UV和CD光谱进行鉴定。提供了大约150种不同的吡喃葡萄糖苷成分的CD光谱数据，以用作鉴定未知衍生物的参考光谱。基于对每个（溴苯甲酰化）寡糖进行糖苷裂解的乙酰分解/溴化反应，已经开发了将寡糖转化为带有4-溴苯甲酸酯和4-甲氧基肉桂酸酯发色团的单糖亚基的方法。该方法为常规的寡糖甲基化分析提供了另一种方法。
• Quinofuracins A–E, Produced by the Fungus <i>Staphylotrichum boninense</i> PF1444, Show p53-Dependent Growth Suppression
  作者：Daisuke Tatsuda、Isao Momose、Tetsuya Someno、Ryuichi Sawa、Yumiko Kubota、Masatomi Iijima、Takao Kunisada、Takumi Watanabe、Masakatsu Shibasaki、Akio Nomoto

  DOI：10.1021/np500581m

  日期：2015.2.27

  Quinofuracins A-E, novel anthraquinone derivatives containing beta-D-galactofuranose that were isolated from the fungus Staphylotrichum boninense PF1444, induced p53-dependent cell death in human tumor cells. The structures of quinofuracins A-E, including absolute configurations, were elucidated by extensive spectroscopic analysis and chemical transformation studies. Quinofuracins were classified into three groups according to the aglycone moieties. 5'-Oxoaverantin was present in quinofuracins A-C, whereas averantin and versicolorin B were identified in quinofuracins D and E, respectively. These quinofuracins induced p53-dependent growth suppression in human glioblastoma LNZTA3 cells.
• US5492836A
  申请人：——

  公开号：US5492836A

  公开（公告）日：1996-02-20
• [EN] METHOD FOR DETERMINING THE STRUCTURE OF OLIGOSACCHARIDE LINKAGES AND AUTOMATED INSTRUMENTATION THEREFOR
  申请人：THE TRUSTEES OF COLUMBIA UNIVERSITY IN THE CITY OF NEW YORK

  公开号：WO1991007649A1

  公开（公告）日：1991-05-30

  (EN) The invention provides a method for determining the structure of a carbohydrate sample, comprising perbenzoylating a carbohydrate sample with a perbenzoylating agent to protect free hydroxyl groups in the carbohydrate sample; cleaving the glycosidic linkages of the perbenzoylated carbohydrate sample by contacting the carbohydrate sample with an amount of BrCH2COBr/H2O effective to cleave the carbohydrate sample; treating the resulting product with AgOAc and methanol or AgOTf/TMU and methanol to effect glycosidation; treating the resulting product with thiourea to remove bromoacetate groups; subjecting the resulting product to effect methoxycinnamoylation of free hydroxyl groups; separating the resulting benzoates with high-pressure liquid chromatography; performing mass, ultraviolet and circular dichroic spectroscopy on the separated benzoates; and comparing the spectra so obtained with reference spectra or calculated values to identify the structure of the carbohydrate. The invention also provides an apparatus for automatically determining the structure of a carbohydrate molecule such as an oligosaccharide.(FR) L'invention présente un procédé de détermination de la structure d'un échantillon de glucide, consistant à perbenzoyler un échantillon de glucide à l'aide d'un agent perbenzoylant afin de protéger les groupes hydroxyle libres se trouvant dans l'échantillon de glucide; à cliver les liaisons glycosidiques de l'échantillon de glucide perbenzoylé, par mise en contact de l'échantillon de glucide avec une quantité de BrCH2COBr/H2O efficace pour cliver l'échantillon de glucide, à traiter le produit ainsi obtenu à l'aide d'AgOAc et de méthanol ou d'AgOTf/TMU et de méthanol afin de procéder à une glycosidation; à traiter le produit ainsi obtenu à l'aide de thio-urée afin d'éliminer les groupes bromoacétate; à soumettre le produit ainsi obtenu à une méthoxycinnamoylation de groupes hydroxyle libres; à séparer les benzoates obtenus par chromatographie liquide sous haute pression; à procéder à une spectroscopie dichroïque de masse, ultraviolette et circulaire sur les benzoates séparés; et à comparer les spectres ainsi obtenus avec des spectres de référence ou des valeurs calculées afin d'identifier la structure du glucide. L'invention concerne également un appareil de détermination automatique de la structure d'une molécule de glucide telle qu'un oligosaccharide.