heptakis(6-S-β-D-glucopyranosyl-6-thio)cyclomaltoheptaose

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: heptakis(6-S-β-D-glucopyranosyl-6-thio)cyclomaltoheptaose
• 英文别名: (1S,3S,5S,6S,8S,10S,11S,13S,15S,16S,18S,20S,21S,23S,25S,26S,28S,30S,31S,33S,35S,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30,35-heptakis[[(2S,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]sulfanylmethyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecol
• 化学式: C₈₄H₁₄₀O₆₃S₇
• 分子量: 2382.46
• InChiKey: LDRJKZXDEAXBGI-CCGJTMSASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -20.6
• 重原子数：
  154
• 可旋转键数：
  28
• 环数：
  28.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  1220
• 氢给体数：
  42
• 氢受体数：
  70

反应信息

• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 甲醇 、 sodium methylate 作用下， 反应 12.0h， 以93%的产率得到heptakis(6-S-β-D-glucopyranosyl-6-thio)cyclomaltoheptaose
  参考文献：
  名称：

  Synthesis of Per-Glycosylated β-Cyclodextrins Having Enhanced Lectin Binding Affinity

  摘要：

  A cyclomaltooligosaccharide containing seven alpha-(1-->4)-D-glucopyranosyl units (beta-cyclodextrins) was transformed into heptakis 6-deoxy-6-iodo (13) and heptakis 6-amino-6-deoxy (25) derivatives using known procedures. Compound 13 was peracetylated and condensed in one pot with the known peracetylated pseudothiouronium salts of beta-D-glucopyranose (4), B-D-galactopyranose (5), or beta-D-N-acetylglucopyranosylsamine (6) or with alpha-D-1-deoxy-1-thiomannopyranose (8) using cesium carbonate in dimethylformamide, Alternatively, peracetylated 4-aminophenyl-alpha-D-mannopyranoside (9) was transformed into either extended pseudothiouronium 11 following N-chloroacetylation and nucleophilic substitution by thiourea or into 4-isothiocyanatophenyl alpha-D-mannopyranoside 12 using thiophosgene. Each of the four thiolated sugar derivatives 4-6 or 8 were also coupled to heptakis chloroacetamido beta-CD 26 obtained from heptakis amine 25 after N-chloroacetylation. Further incorporation of a hexamethylenediamine spacer arm onto heptakis iodo beta-CD 13 using thiol derived from mono-Boc derivative 36 and coupling to isothiocyanate 12 after suitable deprotection afforded permannosylated derivative 38. Zemplen de-O-acetylation of all beta-CD derivatives provided water-soluble persubstituted compounds containing D-glucopyranosides (18, 30), D-galactopyranosides (19, 31), D-N-acetylglucosaminides (20, 32), and D-mannopyranosides (22, 24, 34, 39), respectively The compounds were then evaluated for their relative binding properties toward natural carbohydrate binding plant lectins using both microtiter plate competitive inhibition experiments, double sandwich assays using horseradish peroxidase labeled lectins and by turbidimetric assays. The plant lectins from Pisum sativum (pea), Arachis hypogea (peanut), Canavalia ensiformis (Concanavalin A), and Triticum vulgaris (WGA, wheat germ agglutinin) were used for beta-D-glucose, beta-D-galactose, alpha-D-mannose, and beta-D-N-acetylglucosamine, respectively. All persubstituted beta-CDs showed good to excellent inhibitory properties together with abilities to cross-link their analogous plant lectins. The capacity of perglycosylated beta-CDs to anchor both microtiter plate-coated lectins and their corresponding peroxidase-labeled derivatives further confirmed the usefulness of these multivalent neoglycoconjugates in bioanalytical assays.

  DOI：

  10.1021/jo981576y

文献信息

• Inclusion and solubilization properties of 6-S-glycosyl-6-thio derivatives of β-cyclodextrin
  作者：Valérié Lainé、Annie Coste-Sarguet、Andrée Gadelle、Jacques Defaye、Bruno Perly、Florence Djedaïni-Pilard

  DOI：10.1039/p29950001479

  日期：——

  The synthesis and physico-chemical properties of branched beta-cyclodextrins substituted by one or seven thioglycoside units at the primary hydroxy side are described. The solubilities in water of these compounds are strongly increased compared with the parent beta-cyclodextrin although large differences are found between alpha- and beta-anomers, the former exhibiting the larger solubility. The inclusion capacity of these derivatives has been investigated using NMR spectroscopy as the major analytical technique for various host-guest pairs. The apparent discrepancies between the intrinsic solubilities of these host molecules and their ability to solubilize hydrophobic hosts can be explained from geometrical considerations derived from detailed NMR studies. The respective roles of the:side of inclusion, of steric effects and of stabilizing interactions are evidenced and allow an a priori selection of the optimal host derivative for a given guest molecule.
• Synthesis of Per-Glycosylated β-Cyclodextrins Having Enhanced Lectin Binding Affinity
  作者：Juan José García-López、Fernando Hernández-Mateo、Joaquín Isac-García、Jin Mi Kim、René Roy、Francisco Santoyo-González、Antonio Vargas-Berenguel

  DOI：10.1021/jo981576y

  日期：1999.1.1

  A cyclomaltooligosaccharide containing seven alpha-(1-->4)-D-glucopyranosyl units (beta-cyclodextrins) was transformed into heptakis 6-deoxy-6-iodo (13) and heptakis 6-amino-6-deoxy (25) derivatives using known procedures. Compound 13 was peracetylated and condensed in one pot with the known peracetylated pseudothiouronium salts of beta-D-glucopyranose (4), B-D-galactopyranose (5), or beta-D-N-acetylglucopyranosylsamine (6) or with alpha-D-1-deoxy-1-thiomannopyranose (8) using cesium carbonate in dimethylformamide, Alternatively, peracetylated 4-aminophenyl-alpha-D-mannopyranoside (9) was transformed into either extended pseudothiouronium 11 following N-chloroacetylation and nucleophilic substitution by thiourea or into 4-isothiocyanatophenyl alpha-D-mannopyranoside 12 using thiophosgene. Each of the four thiolated sugar derivatives 4-6 or 8 were also coupled to heptakis chloroacetamido beta-CD 26 obtained from heptakis amine 25 after N-chloroacetylation. Further incorporation of a hexamethylenediamine spacer arm onto heptakis iodo beta-CD 13 using thiol derived from mono-Boc derivative 36 and coupling to isothiocyanate 12 after suitable deprotection afforded permannosylated derivative 38. Zemplen de-O-acetylation of all beta-CD derivatives provided water-soluble persubstituted compounds containing D-glucopyranosides (18, 30), D-galactopyranosides (19, 31), D-N-acetylglucosaminides (20, 32), and D-mannopyranosides (22, 24, 34, 39), respectively The compounds were then evaluated for their relative binding properties toward natural carbohydrate binding plant lectins using both microtiter plate competitive inhibition experiments, double sandwich assays using horseradish peroxidase labeled lectins and by turbidimetric assays. The plant lectins from Pisum sativum (pea), Arachis hypogea (peanut), Canavalia ensiformis (Concanavalin A), and Triticum vulgaris (WGA, wheat germ agglutinin) were used for beta-D-glucose, beta-D-galactose, alpha-D-mannose, and beta-D-N-acetylglucosamine, respectively. All persubstituted beta-CDs showed good to excellent inhibitory properties together with abilities to cross-link their analogous plant lectins. The capacity of perglycosylated beta-CDs to anchor both microtiter plate-coated lectins and their corresponding peroxidase-labeled derivatives further confirmed the usefulness of these multivalent neoglycoconjugates in bioanalytical assays.