melibiose octaacetate | 23846-69-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: melibiose octaacetate
• 英文别名: 1,2,3,4,2',3',4',6'-octa-O-acetyl-D-melibiose；D-melibiose peracetate；(2,3,4,6-tetra-O-acetyl-α-D-galactopyranosyl)-(1-6)-O-(1,2,3,4-tetra-O-acetyl)-D-glucopyranoside；Gal2Ac3Ac4Ac6Ac(a1-6)Glc1Ac2Ac3Ac4Ac；[(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-[[(2R,3R,4S,5R)-3,4,5,6-tetraacetyloxyoxan-2-yl]methoxy]oxan-2-yl]methyl acetate
• CAS: 23846-69-7
• 化学式: C₂₈H₃₈O₁₉
• 分子量: 678.598
• InChiKey: GNTLGGDVHFXGLI-AFDVLSLDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  47
• 可旋转键数：
  20
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  238
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  melibiose octaacetate 在 氢溴酸 、 溶剂黄146 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以25%的产率得到acetobromomelibiose
  参考文献：
  名称：

  激发态钯催化 1,2-自旋中心转移可实现碳水化合物的选择性 C-2 还原、氘化和碘化

  摘要：

  激发态催化是一种涉及一种或多种激发态催化物质的过程，已成为有机合成中的强大工具，因为它允许进入激发态反应景观以发现新颖的化学反应性。在此，我们报告了第一个激发态钯催化的 1,2-自旋中心转移反应，该反应能够实现碳水化合物的位点选择性功能化。该策略的特点是反应条件温和，具有高水平的区域和立体选择性，可耐受多种官能团和复杂的分子结构。机理研究表明，一种根本机制涉及杂合钯物种的形成，该杂合钯物种经历1,2-自旋中心转移，然后进行还原、氘化和碘化，以提供功能化的2-脱氧糖。新的反应性将为快速生成天然和非天然碳水化合物提供通用方法。

  DOI：

  10.1021/jacs.0c11209
• 作为产物：
  描述：

  乙酸酐 、 6-O-alpha-D-吡喃半乳糖基-D-葡萄糖 在 吡啶 、 4-二甲氨基吡啶 作用下， 以94%的产率得到melibiose octaacetate
  参考文献：
  名称：

  Non-Natural glycosphingolipids and structurally simpler analogues bind HIV-1 recombinant Gp120

  摘要：

  Interactions of recombinant gp120 (rgp120) with non-natural glycosphingolipids (GSLs) and structurally simpler analogues have been studied using a competitive adhesion assay. Conjugates of cellobiosyl ceramide and melibiosyl ceramide were synthetically prepared as water-soluble GSL analogues. These ligands were screened against a panel of biologically relevant analogues, and the results show that their interactions with rgp120 are comparable to natural cellular receptors. Glycolipid interactions with rgp120 were probed further by the synthesis and testing of structurally simpler analogues that were obtained by reductive amination of lactose, cellobiose, and melibiose with a biotinylated amino ethylene glycol moiety. RGp120 did not recognize conjugates lacking a lipid component. However. palmitoylation of the secondary amino alditols yielded compounds with comparable rgp120 affinity to the natural cellular receptor. galactosyl ceramide (GalCer). Taken together, the SAR showed that both a hydrophobic and it hydrophilic component are required for rgp120 recognition. Moreover. structural variability in the carbohydrate headgroup did not significantly alter rgp120 recognition indicating that this interaction is not highly specific. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0968-0896(01)00325-x

文献信息

• Glycosyl Coumarin Carbonic Anhydrase IX and XII Inhibitors Strongly Attenuate the Growth of Primary Breast Tumors
  作者：Nadia Touisni、Alfonso Maresca、Paul C. McDonald、Yuanmei Lou、Andrea Scozzafava、Shoukat Dedhar、Jean-Yves Winum、Claudiu T. Supuran

  DOI：10.1021/jm200983e

  日期：2011.12.22

  inhibition of the zinc enzyme carbonic anhydrase (CA, EC 4.2.1.1). These coumarins were very weak or ineffective as inhibitors of the housekeeping, offtarget isoforms CA I and II, but some of them inhibited tumor-associated CA IX and XII in the low nanomolar range. They also significantly inhibited the growth of primary tumors by the highly aggressive 4T1 syngeneic mouse mammary tumor cells at 30 mg/kg, constituting

  合成了一系列结合了各种糖基部分的7-取代香豆素，并研究了其对锌酶碳酸酐酶的抑制作用（CA，EC 4.2.1.1）。这些香豆素作为管家抑制剂，脱靶亚型CA I和II非常弱或无效，但其中一些在低纳摩尔范围内抑制与肿瘤相关的CA IX和XII。它们还以30 mg / kg的高侵袭性4T1同系小鼠乳腺肿瘤细胞显着抑制了原发性肿瘤的生长，构成了开发概念上新颖的抗癌药物的有趣候选物。由于CA IX在低氧性肿瘤中过表达，并且在正常组织中的表达非常有限，因此此类化合物可用于治疗对经典化学疗法和放射疗法无反应的癌症。
• 1,2-cis Alkyl glycosides: straightforward glycosylation from unprotected 1-thioglycosyl donors
  作者：Bo Meng、Zhenqian Zhu、David C. Baker

  DOI：10.1039/c4ob00626g

  日期：——

  A simple, straightforward 1,2-cis-selective glycosidation method from an unprotected 1-thioglycoside is presented.

  一个简单、直接的1,2-cis-选择性糖苷化方法，从未保护的1-硫代糖苷中呈现。
• Optically Active Cyclophane Receptors for Mono- and Disaccharides: The Role of Bidentate Ionic Hydrogen Bonding in Carbohydrate Recognition
  作者：Anne Sophie Droz、Ulf Neidlein、Sally Anderson、Paul Seiler、François Diederich

  DOI：10.1002/1522-2675(20010815)84:8<2243::aid-hlca2243>3.0.co;2-g

  日期：2001.8.15

  feature very different molecular shapes (Fig. 10). In 1H-NMR binding titrations with mono- and disaccharides (Fig. 13), concentration ranges were chosen to favor 1 : 1 host−guest binding. This stoichiometry was experimentally established by the curve-fitting analysis of the titration data and by Job plots. The titration data demonstrate conclusively that the strength of carbohydrate recognition is enhanced

  描述了一种新的旋光环烷受体家族，用于在竞争性质子溶剂混合物中络合单糖和二糖。大环化合物 (−)-(R,R,R,R)-1 – 4 具有由四个 1,1'-binaphthalene-2,2'-磷酸二酯部分通过桥接在 3,3'-位置形成的预组织结合腔炔属或苯炔属间隔物。四个磷酸二酯基团向结合腔汇聚并提供有效的双齿离子 H 键受体位点（图 2）。1,1'-联萘部分的 7,7'-位上的苄氧基确保纳米尺寸受体的溶解性并防止不希望的聚集。四种环烷的大环框架的构建利用了 Sonogashira 协议的 Pd0 催化的芳基 - 乙炔交叉偶联，和氧化炔属均偶联方法（方案 2 和 8 – 10）。还制备了几种具有一个 1,1'-联萘-2,2'-磷酸二酯部分的裂隙型受体（方案 1、6 和 7）。在目标化合物的合成过程中遇到的一个不希望的副反应是通过 5-endo-dig 环化从 3-ethynylnaphthalene-2-ol
• Selective S-deacetylation inspired by native chemical ligation: practical syntheses of glycosyl thiols and drug mercapto-analogues
  作者：Penghua Shu、Jing Zeng、Jinyi Tao、Yueqi Zhao、Guangmin Yao、Qian Wan

  DOI：10.1039/c5gc00084j

  日期：——

  Highly efficient selective S-deacetylations were achieved by simple transthioesterification under mild basic conditions.

  通过在温和的碱性条件下进行简单的硫代酯基转移，即可实现高效的选择性S-脱乙酰基作用。
• Regioselective Deacetylation of Fully Acetylated Mono- and Di-Saccharides With Hydrazine Hydrate
  作者：R Khan、PA Konowicz、L Gardossi、M Matulova、S Degennaro

  DOI：10.1071/ch9960293

  日期：——

  Selective deacetylation reactions of the peracetylated reducing disaccharides (1), (5), (9), (15), β-D- glucopyranose (17) and 2-acetamido-2-deoxy-β-D-glucopyranose (19), with 1.2 equiv. Of hydrazine hydrate in acetonitrile, gave predominantly the corresponding heptaacetates (2), (6), (10), (16), the tetraacetate (18) and the triacetate (20), with the free hydroxy group at C1. Reaction of (1) with 1.2 equiv. of hydrazine hydrate in N,N- dimethylformamide also afforded the heptaacetate (2), but in lower yield. When reactions of (1), (5) and (9) were performed with 2.5 equiv. of hydrazine hydrate, deacetylation also occurred at other positions to afford the corresponding hexaacetates (3), (7), (11) and (12), with hydroxy groups at C 1,2 or C 1,3, and the pentaacetates (4), (8) and (13), with hydroxy groups at C 1,2,3. Maltose octaacetate (9), in addition, yielded the tetraacetate (14) in which the free hydroxy groups were located at C1,2,2',3. Compound (15) on treatment with 2.5 equiv. of hydrazine hydrate afforded an intractable mixture. The reaction of methyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside (21) with 2.5 equiv. of hydrazine hydrate gave the 3,4,6-triacetate (22), a mixture of the 2,6- and the 3,6-diacetates (23) and (24), respectively, the 4,6-diacetate (25), and the 6-acetate (26).

  过乙酰化还原二糖 (1)、(5)、(9)、(15)、β-D-吡喃葡萄糖 (17) 和 2-乙酰氨基-2-脱氧-β-D-吡喃葡萄糖 (19) 与 1.2 等当量的肼水合物在乙腈中进行选择性脱乙酰化反应，主要得到相应的七乙酸酯 (2)、(6)、(10)、(16)、四乙酸酯 (18)乙腈中的水合肼反应，主要得到相应的七乙酸酯（2）、（6）、（10）、（16）、 四乙酸酯（18）和三乙酸酯（20），其游离羟基位于 C1。将(1)与 1.2 等量的水合肼在 N,N-二甲基甲酰胺中反应，也能得到庚乙酸酯(2)，但产量较低。当用 2.5 等量的水合肼对(1)、(5)和(9)进行反应时，在其他位置也会发生脱乙酰化反应，从而得到相应的六乙酸酯(3)、(7)、(11)和(12)（羟基位于 C 1,2 或 C 1,3）以及五乙酸酯(4)、(8)和(13)（羟基位于 C 1,2,3）。此外，麦芽糖八乙酸酯（9）可生成四乙酸酯（14），其中的游离羟基位于 C1,2,2',3。化合物 (15) 在与 2.5 等量的水合肼处理后，生成了一种难溶于水的混合物。2,3,4,6-O-四乙酰基-α-D-吡喃葡萄糖苷甲酯 (21) 与 2.5 等量的水合肼反应，得到 3,4,6-三乙酸酯 (22)、分别为 2,6- 和 3,6- 二乙酸酯 (23) 和 (24) 的混合物、4,6-二乙酸酯 (25) 和 6- 乙酸酯 (26)。