Phenyl 2,3,6-tri-O-acetyl-4-O-(2,6-di-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-1-thio-β-D-glucopyranoside | 152872-00-9

• 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: Phenyl 2,3,6-tri-O-acetyl-4-O-(2,6-di-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-1-thio-β-D-glucopyranoside
• 英文别名: phenyl (2,6-di-O-acetyl-3,4-di-O-isopropylidene-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；phenyl (2,6-di-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside；[(3aS,4R,6S,7R,7aS)-7-acetyloxy-6-[(2R,3R,4S,5R,6S)-4,5-diacetyloxy-2-(acetyloxymethyl)-6-phenylsulfanyloxan-3-yl]oxy-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methyl acetate
• CAS: 152872-00-9
• 化学式: C₃₁H₄₀O₁₅S
• 分子量: 684.716
• InChiKey: STEFFXCOBQPXMR-DGKCMDHPSA-N

物化性质

• 熔点：
  69-70 °C
• 沸点：
  717.3±60.0 °C(predicted)
• 密度：
  1.35±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  47
• 可旋转键数：
  16
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  203
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为反应物：
  描述：

  Phenyl 2,3,6-tri-O-acetyl-4-O-(2,6-di-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-1-thio-β-D-glucopyranoside 在 溶剂黄146 作用下， 以 水 为溶剂， 以85%的产率得到phenyl (2,6-di-O-acetyl-β-D-galactopyranosyl)-(1->4)-2,3,6-tri-O-acetyl-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Transition State Analysis of Vibrio cholerae Sialidase-Catalyzed Hydrolyses of Natural Substrate Analogues

  摘要：

  A series of isotopically labeled natural substrate analogues (phenyl 5-N-acetyl-alpha-u-neuraminyl-(2 -> 3)-alpha-D-galactopyranosyl-(2 -> 4)-1-thio-beta-D-glucopyranoside; Neu5Ac alpha 2,3Lac beta SPh, and the corresponding 2 -> 6 isomer) were prepared chemoenzymatically in order to characterize, by use of multiple kinetic isotope effect (KIE) measurements, the glycosylation transition states for Vibrio cholerae sialidase-catalyzed hydrolysis reactions. The derived KIEs for Neu5Ac alpha 2,3Lac beta SPh for the ring oxygen (V-18/K), leaving group oxygen (V-18/K), C3-S deuterium (V-D/K-S) and C3-R deuterium (V-D/K-R) are 1.029 +/- 0.002, 0.983 +/- 0.001, 1.034 +/- 0.002, and 1.043 +/- 0.002, respectively. In addition, the KIEs for Neu5Ac alpha 2,6 beta SPh for C3-S deuterium (V-D/K-S) and C3-R deuterium (V-D/K-R) are 1.021 +/- 0.001 and 1.049 +/- 0.001, respectively. The glycosylation transition state structures for both Neu5Ac alpha 2,3Lac beta SPh and Neu5Ac alpha 2,6Lac beta SPh were modeled computationally using the experimental KIE values as goodness of fit criteria. Both transition states are late with largely cleaved glycosidic bonds coupled to pyranosyl ring flattening (H-4(5) half-chair conformation) with little or no nucleophilic involvement of the enzymatic tyrosine residue. Notably, the transition state for the catalyzed hydrolysis of Neu5Ac alpha 2,6 beta SPh appears to incorporate a lesser degree of general-acid catalysis, relative to the 2,3-isomer.

  DOI：

  10.1021/ja208564y
• 作为产物：
  描述：

  乙酰氯 、 phenyl (3,4-di-O-isopropylidene-β-D-galactopyranosyl)-(1->4)-1-thio-β-D-glucopyranoside 在 aluminum oxide 作用下， 以 乙腈 为溶剂， 反应 1.5h， 以92%的产率得到Phenyl 2,3,6-tri-O-acetyl-4-O-(2,6-di-O-acetyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  碳水化合物在Al2O3上的酰化作用：制备部分和完全酰化的碳水化合物衍生物和乙酰化的糖基氯化物

  摘要：

  据报道，使用酰氯和固体支持剂Al2O3对碳水化合物衍生物进行选择性和全O酰化。该协议不需要添加任何碱或活化剂。该方法已经进一步扩展到碳水化合物二醇的选择性酰化和直接从游离还原糖直接制备一锅乙酰化糖基氯的方法。在大多数情况下所获得的产量是极好的。

  DOI：

  10.1016/j.carres.2005.11.035

文献信息

• Synthesis of an Aminooxy Derivative of the GM3 Antigen and Its Application in Oxime Ligation
  作者：Kristopher A. Kleski、Mengchao Shi、Matthew Lohman、Gabrielle T. Hymel、Vinod K. Gattoji、Peter R. Andreana

  DOI：10.1021/acs.joc.0c00320

  日期：2020.12.18

  The anomeric aminooxy GM3 trisaccharide cancer antigen (Neu5Acα2,3Galβ1,4Glcβ-ONH2) has been chemically synthesized using a linear glycosylation approach. The key step involves a highly α(2,3)-stereoselective sialylation to a galactose acceptor. The Neu5Acα2,3Gal intermediate was functionalized as a donor for a [2 + 1] glycosylation, including a glucose acceptor that featured an O-succinimidyl group

  氨氧基GM3三糖癌抗原的异头（Neu5Acα2,3Galβ1,4Glcβ-ONH 2）已经使用线性糖基化的方法化学合成。关键步骤涉及对半乳糖受体的高度α（2,3）-立体选择性唾液酸化。Neu5Acα2,3Gal中间体被功能化为[2 +1]糖基化的供体，其中包括在还原端具有O-琥珀酰亚胺基的氨基葡萄糖作为氨基氧基前体。然后将完全脱保护的异头氨基氧基GM3三糖通过肟连接缀合到免疫相关的两性离子多糖PSA1上。
• Efficient Acetylation of Carbohydrates Promoted by Imidazole
  作者：Pallavi Tiwari、Rishi Kumar、Prakas R. Maulik、Anup Kumar Misra

  DOI：10.1002/ejoc.200500555

  日期：2005.10

  An efficient per-O-acetylation of carbohydrate derivatives and unprotected reducing sugars promoted by imidazole is reported. The reaction conditions have been successfully employed to acetylate carbohydrate derivatives containing acid-susceptible functional groups. In most of the cases the yields obtained were excellent. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

  据报道，由咪唑促进的碳水化合物衍生物和未受保护的还原糖的有效过-O-乙酰化。该反应条件已成功用于乙酰化含有酸敏感官能团的碳水化合物衍生物。在大多数情况下，获得的产率非常好。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Efficient acylation and sulfation of carbohydrates using sulfamic acid, a mild, eco-friendly catalyst under organic solvent-free conditions
  作者：Abhishek Santra、Goutam Guchhait、Anup Kumar Misra

  DOI：10.1039/c1gc15122c

  日期：——

  fast and efficient acylation of carbohydrate derivatives and free sugars using a stoichiometric quantity of acylating agents in the presence of sulfamic acid, an environmentally benign catalyst, under organic solvent-free conditions is reported. Excellent yields in the selective acylation and sulfation of carbohydrate derivatives have also been achieved using sulfamic acid as the catalyst. The reaction

  快速高效 酰化 的 碳水化合物衍生物 在存在以下条件下，使用化学计量的酰化剂制备游离糖和游离糖 氨基磺酸，对环境无害 催化剂，在有机 溶剂-无条件的报道。选择性的酰化和硫酸化硫酸具有优异的收率碳水化合物衍生物 也已经通过使用 氨基磺酸 作为 催化剂。反应速度快，收率优异。
• Pouilly, P. de; Chenede, A.; Mallet, J.-M., Bulletin de la Societe Chimique de France, 1993, vol. 130, # 3, p. 256 - 265
  作者：Pouilly, P. de、Chenede, A.、Mallet, J.-M.、Sinay, P.

  DOI：——

  日期：——
• Fast oxidation of thioglycosides to glycosyl sulfones using KMnO4/CuSO4·5H2O under neutral reaction conditions
  作者：Geetanjali Agnihotri、Anup Kumar Misra

  DOI：10.1016/j.carres.2005.11.025

  日期：2006.2

  A rapid oxidation of thioglycosides to glycosyl sulfones has been achieved using a combination of KMnO4 and CuSO(4)center dot 5H(2)O in acetonitrile and water. This reaction protocol has many advantages compared to other methods available for this transformation, including compatibility with acid and base labile functional groups used for the protection of carbohydrates, high yields, fast reaction times, and moderate reaction temperatures. The yields obtained were excellent in all cases. (c) 2005 Elsevier Ltd. All rights reserved.