hexakis-(2,3,6-tri-O-benzyl)-α-cyclodextrin

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: hexakis-(2,3,6-tri-O-benzyl)-α-cyclodextrin
• 英文别名: perbenzylated α-cyclodextrin；(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31S,32R,33S,34R,35S,36R,37S,38R,39S,40R,41S,42R)-31,32,33,34,35,36,37,38,39,40,41,42-dodecakis(phenylmethoxy)-5,10,15,20,25,30-hexakis(phenylmethoxymethyl)-2,4,7,9,12,14,17,19,22,24,27,29-dodecaoxaheptacyclo[26.2.2.23,6.28,11.213,16.218,21.223,26]dotetracontane
• 化学式: C₁₆₂H₁₆₈O₃₀
• 分子量: 2595.1
• InChiKey: WYVWTZCPTCOEGW-ROINKBIGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  23.7
• 重原子数：
  192
• 可旋转键数：
  60
• 环数：
  26.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  277
• 氢给体数：
  0
• 氢受体数：
  30

反应信息

• 作为反应物：
  描述：

  hexakis-(2,3,6-tri-O-benzyl)-α-cyclodextrin 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 、 甲酸 为溶剂， 生成 α-环糊精
  参考文献：
  名称：

  Total synthesis of α-cyclodextrin

  摘要：

  DOI：

  10.1016/0008-6215(85)85239-3
• 作为产物：
  描述：

  在 silver trifluoromethanesulfonate 、 tin(ll) chloride 作用下， 以 乙醚 、 1,2-二氯乙烷 为溶剂， 以21%的产率得到hexakis-(2,3,6-tri-O-benzyl)-α-cyclodextrin
  参考文献：
  名称：

  Total synthesis of α-cyclodextrin

  摘要：

  DOI：

  10.1016/0008-6215(85)85239-3

文献信息

• Synthesis of regioselectively and uniformly modified maltoheptaose derivatives from cyclomaltoheptaose precursors
  作者：David Lesur、Abdoulaye Gassama、Vincent Moreau、Serge Pilard、Florence Djedaïni-Pilard

  DOI：10.1016/j.carres.2005.01.021

  日期：2005.5

  tathiomaltoheptaose derivatives were prepared by acetolysis of the corresponding per-C-6-modified beta-cyclodextrin derivatives. The rapid and convenient structural characterisation of all of the modified oligosaccharides by ESIMS is described.

  通过乙酰水解制备庚烷氧基-6（I-VII）-卤代，叠氮基和庚-6（I-VII）S-庚（N-Boc-2-氨基）乙基-6（I-VII）-庚硫代麦芽七糖衍生物。相应的经C-6修饰的β-环糊精衍生物的制备。描述了通过ESIMS对所有修饰的寡糖进行快速方便的结构表征。
• One-pot synthesis of hexias (6-O-acryl) cyclodextrin derivatives at room temperature
  作者：Yanli Cui、Shanshan Xu、Jianwei Mao

  DOI：10.1007/s10847-015-0505-z

  日期：2015.10

  A mild one-pot synthesis of hexias (6-O-acryl) cyclodextrin derivatives from per-O-benzyl-cyclodextrin was described. It was at room temperature that a regioselective conversion from benyl groups on the primary rim of cyclodextrin to the corresponding acryl groups was achieved with BF3·Me2O as catalyst and acrylic anhydride or acrylic chloride as acylating agent. The reaction was successfully applied in 6-O-acryl regioselective introduction from benzyl 2,3,4,6-tetra-O-benzyl-β-mannopyranoside as well. The products obtained can be valuable precursors for the thiol–ene click reaction or other further modification of carbohydrates.

  描述了一种温和的一锅法合成六元环糊精衍生物的方法，该方法从全-O-苄基环糊精出发，在室温下以BF3·Me2O为催化剂，丙烯酸酐或丙烯酰氯为酰化剂，实现了环糊精初级边缘苄基向相应丙烯酰基的选择性转化。该反应也成功应用于从苄基-2,3,4,6-四-O-苄基-β-甘露吡喃糖苷出发的6-O-丙烯酰基选择性引入。所得产物可作为巯基-烯点击反应或其他碳水化合物进一步修饰的有价值的中间体。
• 一种区域选择性合成6-O-丙烯酰基糖类衍生 物的方法
  申请人：浙江大学

  公开号：CN104387426B

  公开（公告）日：2018-04-24

  本发明公开了一种区域选择性合成6‑O‑丙烯酰基糖类衍生物的方法，以全苄基保护的环糊精、或单糖、或二糖及其衍生物为底物，以有机溶剂为溶剂，在催化剂和酰化剂作用下，经低温搅拌，在温和的反应条件下一锅法直接将全苄基糖伯位的苄基转化为丙烯酰基。本发明高效的区域选择性合成6‑O‑丙烯酰基糖类衍生物的方法，符合绿色化学特点，为糖类衍生物大规模生成，继而应用在人类健康方面奠定了基础，还适用于单糖，或二糖的伯位丙烯酰基的区域选择性取代反应，有利糖化学应用的扩展。
• Towards the sequence-specific multivalent molecular recognition of cyclodextrin oligomers
  作者：Michael Kurlemann、Bart Jan Ravoo

  DOI：10.3762/bjoc.10.253

  日期：——

  Sequence-specific multivalent molecular recognition has been recognized to play a major role in biological processes. Furthermore, sequence-specific recognition motifs have been used in various artificial systems in the last years, e.g., to emulate biological processes or to build up new materials with highly specific recognition domains. In this article, we present the preparation of cyclodextrin (CD)-based strands and complementary and non-complementary strands modified with guest molecules and the investigation of their complexation behavior towards each other by isothermal titration calorimetry (ITC). As complementary binding motifs n-butyl and α-CD and adamantane and β-CD were selected. It was found that it is possible to realize sequence-specific molecular recognition by the use of host–guest chemistry, but the recognition motifs as well as the linkages have to be chosen very carefully. In the case of trivalent systems one adamantane moiety must be included to induce preferred formation of 1:1 adducts. Due to the too weak interaction between n-butyl and α-CD these systems have a negative chelate cooperativity and open adducts are preferentially formed. As soon as two adamantane moieties are present, the complementary systems have a positive chelate cooperativity and double-stranded structures are favored over open adducts. In this system the n-butyl moiety provides insufficient discrimination towards α- and β-CD and no sequence specificity is observed. By the combination of three adamantane moieties sequence specificity can be generated. Exclusively with the complementary CD sequence double-stranded structures are formed, with non-complementary strands aggregates of higher stoichiometry are generated.

  特异性序列多价分子识别在生物过程中发挥重要作用。此外，近年来，序列特异性识别基序已被用于各种人工系统中，例如，模拟生物过程或构建具有高度特异性识别结构域的新材料。在本文中，我们介绍了基于环糊精（CD）的链和修饰有客体分子的互补和非互补链的制备，并通过等温滴定量热法（ITC）研究它们之间的络合行为。作为互补结合基序，选择了n-丁基和α-CD以及脱氢脂肪烷和β-CD。发现通过使用宿主-客体化学可以实现特异性序列分子识别，但识别基序以及连接必须非常谨慎选择。在三价系统中，必须包含一个脱氢脂肪烷基团以诱导首选形成1:1加合物。由于n-丁基和α-CD之间的相互作用过弱，这些系统具有负螯合协同性，优先形成开放的加合物。一旦存在两个脱氢脂肪烷基团，互补系统具有正螯合协同性，双链结构优于开放的加合物。在这个系统中，n-丁基基团对α-CD和β-CD提供的区分不足，没有观察到序列特异性。通过三个脱氢脂肪烷基团的组合，可以产生序列特异性。仅与互补CD序列一起形成双链结构，而与非互补链形成高摩尔配位聚集体。
• Substrate structure governs maximum rate of catalysis exerted by cyclodextrin oxidase chemzymes
  作者：Jeannette Bjerre、Mikael Bols

  DOI：10.1007/s10847-010-9774-8

  日期：2011.4

  highly important factor governing how effectively the oxidation reaction can be catalyzed. Amino acid-type substrates were not prone to catalysis, which yields new information about the limits of CD catalysis. Aniline showed some non-quantifiable catalysis, but for quinones and benzyl alcohols no net catalysis was detected. For aminophenol oxidation, o-aminophenols are far better substrates than p-aminophenols

  选择性修饰的 α- 和 β- 环糊精酮或醛在各种小的亲脂性底物上充当人工氧化酶。底物的结构是决定氧化反应催化效率的非常重要的因素。氨基酸型底物不易被催化，这产生了关于 CD 催化极限的新信息。苯胺显示出一些不可量化的催化作用，但对于醌和苯甲醇，未检测到净催化作用。对于氨基苯酚氧化，邻氨基苯酚是比对氨基苯酚更好的底物。CD 催化的反应遵循 Michaelis-Menten 动力学，涉及底物的 CD 腔结合和底物识别，因此包含许多天然酶催化的标志。共氧化剂 H2O2 与 CD 催化羰基的强结合是底物随后氧化的先决条件，因此，H2O2 与 β-CD 二醛的结合显示出很强的结合力（Kd = 1.4 mM）。β-CD 6A,6D-二酮与 H2O2 的结合比醛弱，因此是一种效率较低的氧化酶。适用于 CD 化学酶催化的广泛底物为合成生物学的未来范围带来了乐观。