4-甲基伞形酮2,3,4,6-四-O-乙酰基-beta-D-吡喃半乳糖苷 | 6160-79-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 香豆素及其衍生物
• 中文名称: 4-甲基伞形酮2,3,4,6-四-O-乙酰基-beta-D-吡喃半乳糖苷
• 英文名称: 4-methylumbelliferyl 2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside
• 英文别名: 2H-1-Benzopyran-2-one, 4-methyl-7-((2,3,4,6-tetra-O-acetyl-beta-D-galactopyranosyl)oxy)-；[(2R,3S,4S,5R,6S)-3,4,5-triacetyloxy-6-(4-methyl-2-oxochromen-7-yl)oxyoxan-2-yl]methyl acetate
• CAS: 6160-79-8
• 化学式: C₂₄H₂₆O₁₂
• 分子量: 506.463
• InChiKey: GBHHLVBZMNCURY-HYPCABPSSA-N

物化性质

• 溶解度：
  可溶于氯仿

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  36
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  150
• 氢给体数：
  0
• 氢受体数：
  12

制备方法与用途

用途：用于荧光法β-半乳糖苷酶测定的保护性基质。

反应信息

• 作为反应物：
  描述：

  4-甲基伞形酮2,3,4,6-四-O-乙酰基-beta-D-吡喃半乳糖苷 在 咪唑 、 4 A molecular sieve 、 四乙基溴化铵 、 四丁基氟化铵 、 sodium methylate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 68.5h， 生成 4-methylumbelliferyl 3'-O-(2'',3'',4''-tri-O-acetyl-α-L-fucopyranosyl)-β-D-galactopyranoside
  参考文献：
  名称：

  Stereoselective synthesis of α-L-Fucp-(1,2)- and -(1,3)-β-D-Galp(1)-4-methylumbelliferone using glycosyl donor substituted by propane-1,3-diyl phosphate as leaving group

  摘要：

  合成双糖α-L-岩藻糖-(1,2)-和α-L-岩藻糖-(1,3)-β-D-半乳糖-(1)-4-甲基伞花素作为岩藻糖苷酶底物，通过用TMSOTf激活2,3,4-三-O-乙酰基和2,3,4,6-四-O-乙酰基α,β-L-岩藻糖和-D-半乳糖基丙烷-1,3-二醇磷酸盐的异头中心，并对4-甲基伞花素β-D-半乳糖苷进行了最小保护。

  DOI：

  10.1039/b002754p
• 作为产物：
  描述：

  beta-D-半乳糖五乙酸酯 在 四丁基溴化铵 、 氢溴酸 、 溶剂黄146 、 sodium hydroxide 作用下， 以 氯仿 、 水 为溶剂， 反应 20.0h， 生成 4-甲基伞形酮2,3,4,6-四-O-乙酰基-beta-D-吡喃半乳糖苷
  参考文献：
  名称：

  一种4-甲基伞形酮基-β-D-吡喃半乳糖苷的制 备方法

  摘要：

  本发明公开了一种4-甲基伞形酮基-β-D-吡喃半乳糖苷的制备方法。其包括以下步骤：第一步，4-甲基伞形酮的制备；第二步，四乙酰基-α-D-吡喃半乳糖的制备；第三步，4-甲基伞形酮基-2,3,4,6-四乙酰基-β-D-吡喃半乳糖苷的制备；第四步，4-甲基伞形酮基-β-D-吡喃半乳糖苷的制备。本发明提供的方法反应条件温和，室温下反应即可；无需使用重金属盐类，环境友好；产率高，糖苷化一步产率可达73.1%，总产率达32.9%。微生物实验证明，产品和进口底物效果相当，可以替代进口产品。

  公开号：

  CN103897001B

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。
• Natural sialoside analogues for the determination of enzymatic rate constants
  作者：Deepani Indurugalla、Jacqueline N. Watson、Andrew J. Bennet

  DOI：10.1039/b613909d

  日期：——

  Two isomeric 4-methylumbelliferyl-α-D-N-acetylneuraminylgalactopyranosides (1 and 2) were synthesised. These compounds contain either the natural α-2,3 or α-2,6 sialyl–galactosyl linkages, as well as an attached 4-methylumbelliferone for convenient detection of their hydrolyses. These compounds were designed as natural sialoside analogues to be used in a continuous assay of sialidase activity, where the sialidase-catalysed reaction is coupled with an exo-β-galactosidase-catalysed hydrolysis of the released galactoside to give free 4-methylumbelliferone. The kinetic parameters for 1 and 2 were measured using the wild-type and nucleophilic mutant Y370G recombinant sialidase from Micromonospora viridifaciens. Kinetic parameters for these analogues measured using the new continuous assay were in good agreement with the parameters for the natural substrate, 3′-sialyl lactose. Given the selection of commercially available exo-β-galactosidases that possess a variety of pH optima, this new method was used to characterise the full pH profile of the wild-type sialidase with the natural sialoside analogue 1. Thus, use of these new substrates 1 and 2 in a continuous assay mode, which can be detected by UV/Vis or fluorescence spectroscopy, makes characterisation of sialidase activity with natural sialoside linkages much more facile.

  我们合成了两种异构的 4-甲基伞形酮基-α-D-N-乙酰神经氨酰半乳糖苷（1 和 2）。这些化合物含有天然的 α-2,3 或 α-2,6 水杨酰-半乳糖苷链节，以及附着的 4-甲基伞形酮，便于检测其水解情况。这些化合物被设计为天然半乳糖苷类似物，可用于半乳糖苷酶活性的连续检测，其中半乳糖苷酶催化的反应与外-β-半乳糖苷酶催化的半乳糖苷释放水解结合在一起，生成游离的 4-甲基伞形酮。1 和 2 的动力学参数是使用野生型和亲核突变体 Y370G 重组硅糖苷酶测定的。使用新的连续测定法测得的这些类似物的动力学参数与天然底物 3′-硅烷基乳糖的参数非常一致。鉴于市售的外-β-半乳糖苷酶具有多种最适 pH 值，这种新方法可用于鉴定野生型硅氨糖苷酶与天然硅氨糖苷类似物 1 的整个 pH 值曲线。因此，在可通过紫外/可见光或荧光光谱检测的连续测定模式中使用这些新底物 1 和 2，可以更方便地鉴定天然半乳糖苷连接物的半乳糖苷酶活性。
• Application of silver N-heterocyclic carbene complexes in O-glycosidation reactions
  作者：Ian J. Talisman、Vineet Kumar、Jeffrey R. Deschamps、Mark Frisch、Sanjay V. Malhotra

  DOI：10.1016/j.carres.2011.07.025

  日期：2011.11

  We report the efficient O-glycosidation of glycosyl bromides with therapeutically relevant acceptors facilitated by silver N-heterocyclic carbene (Ag-NHC) complexes. A set of four Ag-NHC complexes was synthesized and evaluated as promoters for glycosidation reactions. Two new bis-Ag-NHC complexes derived from ionic liquids 1-benzyl-3-methyl-1H-imidazolium chloride and 1-(2-methoxyethyl)-3-methylimidazolium chloride were found to efficiently promote glycosidation, whereas known mono-Ag complexes of 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride and 1,3-bis(2,6-di-isopropylphenyl)imidazolium chloride failed to facilitate the reaction. The structures of the promoters were established by X-ray crystallography and these complexes were employed in the glycosidation of different glycosyl bromide donors with biologically valuable acceptors, such as estrone, estradiol, and various flavones. The products were obtained in yields considered good to excellent, and all reactions were highly selective for the 13 isomer regardless of neighboring group effects. (C) 2011 Elsevier Ltd. All rights reserved.
• Constantzas; Kocourek, Collection of Czechoslovak Chemical Communications, 1959, vol. 24, p. 1099,1102
  作者：Constantzas、Kocourek

  DOI：——

  日期：——
• Stereoselective synthesis of α-L-Fucp-(1,2)- and -(1,3)-β-D-Galp(1)-4-methylumbelliferone using glycosyl donor substituted by propane-1,3-diyl phosphate as leaving group
  作者：Hariprasad Vankayalapati、Gurdial Singh

  DOI：10.1039/b002754p

  日期：——

  The synthesis of the disaccharides α-L-Fucp-(1,2)- and α-L-Fucp-(1,3)-β-D-Galp(1)-4-methylumbelliferone as fucosidase substrates was accomplished by activation of the anomeric centre of 2,3,4-tri-O-acetyl- and 2,3,4,6-tetra-O-acetyl-α,β-L-fuco- and -D-galactopyranosyl propane-1,3-diyl phosphates with TMSOTf and with minimal protection of 4-methylumbelliferyl β-D-galactopyranoside.

  合成双糖α-L-岩藻糖-(1,2)-和α-L-岩藻糖-(1,3)-β-D-半乳糖-(1)-4-甲基伞花素作为岩藻糖苷酶底物，通过用TMSOTf激活2,3,4-三-O-乙酰基和2,3,4,6-四-O-乙酰基α,β-L-岩藻糖和-D-半乳糖基丙烷-1,3-二醇磷酸盐的异头中心，并对4-甲基伞花素β-D-半乳糖苷进行了最小保护。