2,3,4,6-tetra-O-acetyl-β-D-galactopyranose | 70191-05-8

• 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: 2,3,4,6-tetra-O-acetyl-β-D-galactopyranose
• 英文别名: 2,3,4,6-tetra-O-acetyl-D-galactopyranose；2,3,4,6-Tetra-o-acetyl-beta-d-galactopyranose；[(2R,3S,4S,5R,6R)-3,4,5-triacetyloxy-6-hydroxyoxan-2-yl]methyl acetate
• CAS: 70191-05-8
• 化学式: C₁₄H₂₀O₁₀
• 分子量: 348.307
• InChiKey: IEOLRPPTIGNUNP-MBJXGIAVSA-N

物化性质

• 熔点：
  145 °C
• 沸点：
  0.130 °C(Press: 0.0007 Torr)
• 密度：
  1.33±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  24
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  135
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-β-D-galactopyranose 在 palladium on activated charcoal 4 A molecular sieve 、 氢气 、 sodium methylate 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， -30.0~20.0 ℃ 、344.74 kPa 条件下， 反应 22.0h， 生成 3-aminopropyl β-D-galactopyranoside
  参考文献：
  名称：

  Synthesis and Enzyme-Specific Activation of Carbohydrate−Geldanamycin Conjugates with Potent Anticancer Activity

  摘要：

  Geldanamycin (GA) is a potent anticancer antibiotic that inhibits Hsp90. Its potential clinical utility is hampered by its severe toxicity. To alleviate this problem, we synthesized a series of carbohydrate - geldanamycin conjugates for enzyine-specific activation to increase tumor selectivity. The conjugation was carried out at the C-17-position of GA. Their anticancer activity was tested in a number of cancer cell lines. The enzyme-specific activation of these conjugates M ion was evaluated with beta-galactosidase and beta-glucosidase. Evidently. glycosylation of C-17-pasition converted GA to an inactive prodrug before enzyme cleavage. Glucose-GA, as positive control, showed anticancer activity with IC50 of 70.2- 380.9 nM in various cancer cells by beta-glucocsidase activation inside of the tumor cells, which was confirmed by 3-fold inhibition using beta-glucasidase. specific inhibitor [2,5-dihydroxyniethy-3,4-dihydroxypyrrolidine (DMDP)]. Compared to glucose- GA, galactose- and lactose-GA conjugates exhibited much less activity with IC50 greater than 8000-25 000 nM. However, when galactose- and lactose-GA, were incubated with beta-galactosidase in the cells, their anticancer activity was enhanced by 3- to 40-fold. The results suggest, that GA can be inactivated by glycosylation of C-17-position and reactivated for anticancer activity by beta-galactosidase. Therefore, galactose-GA can be exploited in antibody-directed enzyme prodrug therapy (ADEPT) with beta-galactosidase for enzyme-specific activation in tumors. to increase tumor selectivity.

  DOI：

  10.1021/jm049693a
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 mercury dichloride 、 mercury(II) oxide 作用下， 以 丙酮 为溶剂， 反应 48.0h， 以71%的产率得到2,3,4,6-tetra-O-acetyl-β-D-galactopyranose
  参考文献：
  名称：

  氯化汞和氧化汞对过酰吡喃糖的区域选择性 1-O-酰基水解

  摘要：

  过酰基化的吡喃葡萄糖的区域选择性 1-O-酰基水解 Th t Sambaiah,a Phillip E. Fanwick,b Mark Cushman*aa 普渡大学药物化学和分子药理学系，西拉斐特，印第安纳州 47907，美国 传真 [phone] ; 电子邮件： [e-mail] b 普渡大学化学系，美国印第安纳州西拉斐特 47907 2001 年 1 月 19 日收到；2001 年 3 月 13 日修订

  DOI：

  10.1055/s-2001-16084

文献信息

• Synthesis of an Isotopically-labelled Antarctic Fish Antifreeze Glycoprotein Probe
  作者：Joanna M. Wojnar、Clive W. Evans、Arthur L. DeVries、Margaret A. Brimble

  DOI：10.1071/ch10464

  日期：——

  Antifreeze glycoproteins (AFGPs) are glycosylated polypeptides produced by Antarctic and Arctic fishes, which allow them to survive in seawater at sub-zero temperatures. An investigation into the postulated enteric uptake of AFGP synthesized in the exocrine pancreas of Antarctic fishes required a custom-prepared AFGP probe that incorporated seven isotopically-labelled Ala residues for detection by

  抗冻糖蛋白（AFGP）是南极和北极鱼类产生的糖基化多肽，可以使它们在低于零温度的海水中生存。对南极鱼类外分泌胰腺中合成的AFGP的假定肠摄取的调查，需要定制的AFGP探针，该探针结合了7个同位素标记的Ala残基，用于质谱检测。的AFGPs由重复的三个氨基酸单元（丙氨酸-丙氨酸-苏氨酸），其中，所述苏氨酸残基是糖基化与二糖的β- d -Gal-（1→3）-α- d -GalNAc。同位素标记的AFGP8（1）的合成，以及受保护的糖基化氨基酸构件2的优化合成，已报告。
• 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）。
• Synthesis of 3-O-propargylated betulinic acid and its 1,2,3-triazoles as potential apoptotic agents
  作者：Rabiya Majeed、Payare L. Sangwan、Praveen K. Chinthakindi、Imran Khan、Nisar A. Dangroo、Niranjan Thota、Abid Hamid、Parduman R. Sharma、Ajit K. Saxena、Surrinder Koul

  DOI：10.1016/j.ejmech.2013.03.028

  日期：2013.5

  carried out on betulinic acid, through concise 1,2,3-triazole synthesis via click chemistry approach at C-3position in ring A have been evaluated for their cytotoxic potentiation against nine human cancer cell lines. Most of the derivatives have shown higher cytotoxic profiles than the parent molecule. Two compounds i.e. 31N(2-cyanophenyl)-1H-1,2,3-triazol-4yl}methyloxy betulinic acid (7) and 31N(5-hyd

  目前，来自自然界的细胞毒性剂是抗癌化学疗法的主要手段，因此迫切需要增强抗癌剂库的需求。已通过在A环C-3位的C-3位置通过单击化学方法通过简明的1,2,3-三唑合成对桦木酸进行的化学转化研究，评估了它们对9种人类癌细胞系的细胞毒性增强作用。大多数衍生物显示出比母体分子更高的细胞毒性谱。两种化合物，即3 1 Ñ（2-氰基苯基）-1 ħ 1,2,3-三唑-4-基}甲氧基桦木酸（7）和3 1 Ñ（5-羟基-萘-1-基）-1 ħ - 1,2,3-三唑-4基}甲氧基苯丁酸（13）对白血病细胞系HL-60表现出令人印象深刻的IC 50值（分别为2.5和3.5μM）（效力比白果酸高5至7倍）。从各种生物学终点来看，证明了对细胞迁移和集落形成的抑制，线粒体膜的破坏，随后的DNA片段化和凋亡。
• Novel Galactosylated Poly(ethylene glycol)-Cholesterol for Liposomes as a Drug Carrier for Hepatocyte-Targeting
  作者：Huafang Zhang、Yan Xiao、Shengmiao Cui、Yuefang Zhou、Ke Zeng、Mina Yan、Chunshun Zhao

  DOI：10.1166/jnn.2015.9707

  日期：2015.6.1

  In this study, three types of galactosylated cholesterol (i.e., gal-PEG194-chol, gal-PEG1000-chol and gal-PEG2000-chol) were synthesized with one terminal of polyethylene glycol of various chain lengths conjugated to the galactoside moiety, and the other terminal conjugated to the cholesterol. The galactose-modified liposomes were prepared by thin film-hydration method and doxorubicin (DOX) was loaded to the liposomes by using a ammonium sulfate gradient procedure. The liposomal formulations with galactosylated cholesterol were characterized. Flow cytometry and laser confocal scanning microscopy analyses showed that the galactose-modified liposomes facilitated the intracellular uptake of liposomes into HepG2 via asialoglycoprotein receptor (ASGP-R) mediated endocytosis. Cytotoxicity assay showed that the cell proliferation inhibition effect of galactose-modified liposomes was higher than that of the unmodified liposomes. Additionally, the study on frozen section of liver showed that the galactose-modified liposomes enhanced the intracellular uptake of liposomes into hepatocytes. Taken together, these results suggested that liposomes containing such galactosylated cholesterol (i.e., gal-PEG-chol), had a great potential as drug delivery carriers for hepatocyte-selective targeting.

  在这项研究中，合成了三种类型的半乳糖化胆固醇（即gal-PEG194-chol、gal-PEG1000-chol和gal-PEG2000-chol），它们的一个端基通过不同链长的聚乙二醇与半乳糖基团连接，另一个端基与胆固醇连接。通过薄膜水化法制备了半乳糖修饰的脂质体，并利用硫酸铵梯度法将阿霉素(DOX)装载到脂质体中。对含有半乳糖化胆固醇的脂质体进行了表征。流式细胞术和激光共聚焦扫描显微镜分析显示，半乳糖修饰的脂质体通过脱唾液酸糖蛋白受体(ASGP-R)介导的内吞作用促进了脂质体进入HepG2细胞的细胞内摄取。细胞毒性测定表明，半乳糖修饰脂质体的细胞增殖抑制效果高于未修饰脂质体。此外，对肝脏冷冻切片的研究表明，半乳糖修饰的脂质体增强了脂质体进入肝细胞的细胞内摄取。综上所述，这些结果表明，含有这种半乳糖化胆固醇（即gal-PEG-chol）的脂质体，作为肝细胞选择性靶向药物传递载体具有巨大的潜力。
• SnCl₄- and TiCl₄-Catalyzed Anomerization of Acylated <i>O</i>- and <i>S</i>-Glycosides: Analysis of Factors That Lead to Higher α:β Anomer Ratios and Reaction Rates
  作者：Wayne Pilgrim、Paul V. Murphy

  DOI：10.1021/jo101090f

  日期：2010.10.15

  glucuronic acid or galacturonic acid derivatives were ∼10 to 3000 times faster than those of related glucoside and galactopyranoside counterparts and α:β ratios were generally also higher. Stereoelectronic effects contributed from galacto-configured compounds were up to 2-fold faster than those of corresponding glucosides. The introduction of groups, including protecting groups, which are increasingly electron

  讨论了影响SnCl 4和TiCl 4催化的异构化反应速率和立体选择性的因素的定量，以及这如何影响α- O-和α- S-糖脂的合成。SnCl 4催化的18种底物的β- S-和β- O-糖苷的阴离子化反应遵循一级平衡动力学，得到k f + k r值，其中k f是正向反应的速率常数（β→ α）和k r是逆反应的速率常数（α→β）。比较k f + k r值表明，葡萄糖醛酸或半乳糖醛酸衍生物的反应比相关的葡萄糖苷和吡喃半乳糖苷对应物的反应快约10至3000倍，并且α：β比率通常也更高。由半乳糖配置的化合物产生的立体电子效应比相应的糖苷的高达快2倍。越来越多地释放电子的基团（包括保护基）的引入通常导致速率提高。S-糖苷的异构化速度始终快于相应的O-糖苷。与TiCl 4的反应通常比与SnCl 4的反应更快。端基异构体的比例取决于路易斯酸，路易斯酸的当量数，温度和底物。对于TiCl 4促进的反应，观察到O