mono(2-O-tosyl)heptakis(6-O-tert-butyldimethylsilyl)-β-cyclodextrin | 133117-62-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: mono(2-O-tosyl)heptakis(6-O-tert-butyldimethylsilyl)-β-cyclodextrin
• 英文别名: mono(2-O-tosyl) heptakis(6-O-tert-butyldimethylsilyl)β-cyclodextrin；[(1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40S,41R,42R,43R,44R,45R,46R,47R,48R,49R)-5,10,15,20,25,30,35-heptakis[[tert-butyl(dimethyl)silyl]oxymethyl]-36,37,38,39,40,42,43,44,45,46,47,48,49-tridecahydroxy-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]nonatetracontan-41-yl] 4-methylbenzenesulfonate
• CAS: 133117-62-1
• 化学式: C₉₁H₁₇₄O₃₇SSi₇
• 分子量: 2089.02
• InChiKey: ZBGNRNQPZZJTJS-MJKYRYNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.7
• 重原子数：
  136
• 可旋转键数：
  31
• 环数：
  22.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  509
• 氢给体数：
  13
• 氢受体数：
  37

反应信息

• 作为反应物：
  描述：

  mono(2-O-tosyl)heptakis(6-O-tert-butyldimethylsilyl)-β-cyclodextrin 在 potassium ethoxide 作用下， 以 乙醇 为溶剂， 反应 1.17h， 以87%的产率得到mono(2(A),3(A)-anhydro)-heptakis(6-O-tert-butyldimethylsilyl)-β-CD
  参考文献：
  名称：

  基于环糊精的酶模型。第 1 部分。合成甲苯磺酸盐和衍生自七 (6-O-叔丁基二甲基甲硅烷基)-β-环糊精的环氧化物及其使用 2D NMR 技术的表征。在二级面上功能化环糊精的改进途径

  摘要：

  提出了合成在次级面上具有催化基团的基于环糊精 (CD) 的酶模型的改进路线。衍生自七 (6-O-叔丁基二甲基甲硅烷基)-β-CD 的环氧化物是通过中间体制备的，这些中间体可以通过常规快速色谱法在制备规模上进行纯化。β-环糊精与反应；吡啶中的叔丁基二甲基甲硅烷基氯得到七(6-O-叔丁基二甲基甲硅烷基)-β-CD (1)。在氯仿中用 N-甲苯磺酰基咪唑和 NaOMe 处理 1 得到单（2-O-甲苯磺酰基）七（6-O-叔丁基二甲基甲硅烷基）-β-CD（2），产率为 22%。后者通过用 KOEt 处理顺利转化为单（2A，3A-脱水）七（6-O-叔丁基二甲基甲硅烷基）-β-CD（3），其中一个葡萄糖亚基已转化为甘露环氧化物在回流的乙醇中（87% 产率）。化合物 1、2、和 3 用各种一维和二维核磁共振技术进行了表征。这些结果为催化基团以明确定义的方式连接到环糊精打开了大门。

  DOI：

  10.1139/v91-021
• 作为产物：
  描述：

  七-6-(二甲基-叔-丁基甲硅烷基)-β-环糊精 、 对甲苯磺酰氯 在 吡啶 作用下， 反应 24.0h， 以26%的产率得到mono(2-O-tosyl)heptakis(6-O-tert-butyldimethylsilyl)-β-cyclodextrin
  参考文献：
  名称：

  Efficient Monomodification of the Secondary Hydroxy Groups of β-Cyclodextrin

  摘要：

  DOI：

  10.1021/jo981866e

文献信息

• Cyclodextrin-based enzyme models. Part 1. Synthesis of a tosylate and an epoxide derived from heptakis(6-<i>O</i>-<i>tert</i>-butyldimethylsilyl)-β-cyclodextrin and their characterization using 2D NMR techniques. An improved route to cyclodextrins functionalized on the secondary face
  作者：Marko J. Pregel、Erwin Buncel

  DOI：10.1139/v91-021

  日期：1991.1.1

  heptakis(6-O-tert-butyldimethylsilyl)-β-CD (1). Treatment of 1 with N-tosylimidazole and NaOMe in chloroform gave mono(2-O-tosyl) heptakis(6-O-tert-butyldimethylsilyl)-β-CD (2) in 22% yield. The latter was converted smoothly to mono(2A, 3A-anhydro) heptakis(6-O-tert-butyldimethylsilyl)-β-CD (3), in which one glucose subunit has been converted to a manno-epoxide, by treatment with KOEt in refluxing ethanol (87% yield)

  提出了合成在次级面上具有催化基团的基于环糊精 (CD) 的酶模型的改进路线。衍生自七 (6-O-叔丁基二甲基甲硅烷基)-β-CD 的环氧化物是通过中间体制备的，这些中间体可以通过常规快速色谱法在制备规模上进行纯化。β-环糊精与反应；吡啶中的叔丁基二甲基甲硅烷基氯得到七(6-O-叔丁基二甲基甲硅烷基)-β-CD (1)。在氯仿中用 N-甲苯磺酰基咪唑和 NaOMe 处理 1 得到单（2-O-甲苯磺酰基）七（6-O-叔丁基二甲基甲硅烷基）-β-CD（2），产率为 22%。后者通过用 KOEt 处理顺利转化为单（2A，3A-脱水）七（6-O-叔丁基二甲基甲硅烷基）-β-CD（3），其中一个葡萄糖亚基已转化为甘露环氧化物在回流的乙醇中（87% 产率）。化合物 1、2、和 3 用各种一维和二维核磁共振技术进行了表征。这些结果为催化基团以明确定义的方式连接到环糊精打开了大门。
• Selective Functionalization and Flexible Coupling of Cyclodextrins at the Secondary Hydroxyl Face
  作者：Erik van van Dienst、Bianca H. M. Snellink、Irma von Piekartz、Marcel H. B. Grote Gansey、Fokke Venema、Martinus C. Feiters、Roeland J. M. Nolte、Johan F. J. Engbersen、David N. Reinhoudt

  DOI：10.1021/jo00125a045

  日期：1995.10

  Methods are described for the chemo- and regioselective monofunctionalization of the secondary hydroxyl face of cyclodextrins. Monofunctionalization takes place either by nucleophilic epoxide opening of mono(2(A),3(A)-anhydro)heptakis(6-O-tert-butyldimethylsilyl)-(2(A)S)-beta-cylodextrin by ethylenediamine, lithium azide, or ammonia or by direct monoalkylation of one of the C(2)-hydroxyl groups of heptakis(6-O-tert-butyldimethylsilyl)cyclodextrins with primary alkyl bromides, with cyano-, ethynyl-, or ester-containing functional groups. The latter route enables the synthesis of mono(2(A)-O-(alpha-(4-(aminomethyl)tolyl))hexakis(2(B),2(C),2(D),2(E),2(F),2(G),-O-methyl)heptakis(6-O-tert-butyldimethylsilyl)-beta-cyclodextrin and its 2-aminomethyl isomer. These are lipophilic precursors for cyclodextrin derivatives having one reactive functional group and an enlarged molecular cavity formed by partial methylation of the secondary hydroxyl face. The direct monoalkylation route of the secondary face leaves the structure of the cavity intact, while this is distorted in the route using nucleophilic epoxide opening. Two amino-functionalized cyclodextrins were used for coupling reactions with a monofunctionalized calix[4]arene. In this way water-soluble cyclodextrin derivatives could be obtained of which the secondary faces were flexibly capped with a calix[4]arene moiety.
• Synthesis, Conformation, and Binding Properties of Cyclodextrin Homo- and Heterodimers Connected through Their Secondary Sides
  作者：Fokke Venema、Hubertus F. M. Nelissen、Patrick Berthault、Nicolaos Birlirakis、Alan E. Rowan、Martinus C. Feiters、Roeland J. M. Nolte

  DOI：10.1002/(sici)1521-3765(19981102)4:11<2237::aid-chem2237>3.0.co;2-4

  日期：1998.11.2

  The synthesis of homo- and heterocyclodextrin (CD) dimers, containing two CD moieties that are linked through their secondary sides by aliphatic or 2,2'-bipyridyl spacers is described. In these dimers, the glucose units to which the spacers are linked have been transformed into altrose units. The dimers with an octamethylene spacer show self-complexation of the spacer in one of the CD moieties in aqueous solution, as revealed by H-1 and C-13 NMR spectroscopy. Using high-resolution (600 and 800 MHz) NMR spectroscopy and a variety of 2D NMR techniques, an assignment of nearly all of the H-1 NMR signals of two of the CD dimers was made, affording detailed information about the structure of these compounds in water. The self-inclusion of the spacers leads to lower binding affinities for ditopic guest molecules like p-toluidino-6-naphthalene sulfonate (TNS) derivatives and porphyrins. When a rigid 2,2'-bipyridyl group is used to connect the two CD moieties, self-inclusion of the spacer is not possible. This results in the formation of different complexes with ditopic guest molecules, for example, a 2:2 complex with a porphyrin.The CD heterodimers described in this paper contain an alpha-CD and a beta-CD moiety. These dimers display site-specific binding of guest molecules.
• Efficient Monomodification of the Secondary Hydroxy Groups of β-Cyclodextrin
  作者：Sheng-Hsien Chiu、David C. Myles

  DOI：10.1021/jo981866e

  日期：1999.1.1