6^A,6^D-dialdehydo-β-cyclodextrin | 163016-94-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6^A,6^D-dialdehydo-β-cyclodextrin
• 英文别名: A,D-Diformyl-β-cyclodextrin；(1S,3S,5S,6S,8R,10R,11S,13R,15R,16S,18S,20S,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecahydroxy-10,15,25,30,35-pentakis(hydroxymethyl)-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-5,20-dicarbaldehyde
• CAS: 163016-94-2
• 化学式: C₄₂H₆₆O₃₅
• 分子量: 1130.97
• InChiKey: UBRHNBQJOQLITP-FOUAGVGXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -14.7
• 重原子数：
  77
• 可旋转键数：
  7
• 环数：
  21.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  548
• 氢给体数：
  19
• 氢受体数：
  35

反应信息

• 作为反应物：
  描述：

  6^A,6^D-dialdehydo-β-cyclodextrin 在 sodium hypochlorite 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 5.0h， 生成 5^A,5^D-dicarboxy-β-cyclodextrin
  参考文献：
  名称：

  5A,5D-dicarboxy-β-cyclodextrin derivatives - a route for regioselectively difunctionalized permethyl-β-cyclodextrin

  摘要：

  DOI：

  10.1016/s0040-4039(01)93941-3
• 作为产物：
  描述：

  biphenyl-4,4'-disulfonyl-A,D-capped β-cyclodextrin 在 2,3,5-三甲基吡啶 、 二甲基亚砜 作用下， 反应 1.5h， 以69%的产率得到6^A,6^D-dialdehydo-β-cyclodextrin
  参考文献：
  名称：

  A General Method for the Synthesis of Cyclodextrinyl Aldehydes and Carboxylic Acids

  摘要：

  The selective synthesis of the primary-side monoaldehyde of beta-cyclodextrin, 6-deoxy-6-formyl-beta-cyclodextrin, was accomplished by oxidation of the corresponding tosylate utilizing the Nace reaction (DMSO/collidine). This monoaldehyde was then used as the starting material in several reactions including reduction, addition of NaHSO3, addition of the alpha-nucleophiles hydroxylamine and hydrazine, and reductive amination. Of particular interest is the conversion of the monoaldehyde to the primary side carboxylic acid, 6-deoxy-6-carboxy-beta-cyclodextrin, via bromine oxidation. This general method sequence can be applied to any tosyl derivative of cyclodextrin as demonstrated in the synthesis of beta-cyclodextrin-A,D-dialdehyde and beta-cyclodextrin-A,D-diacid.

  DOI：

  10.1021/jo00114a030

文献信息

• Four Orders of Magnitude Rate Increase in Artificial Enzyme-Catalyzed Aryl Glycoside Hydrolysis
  作者：Fernando Ortega-Caballero、Jeannette Bjerre、Line Skall Laustsen、Mikael Bols

  DOI：10.1021/jo050861w

  日期：2005.9.1

  kcat/kuncat ranging from 4 to 7100. Hydrolysis of a phenyl β-d-glucoside or the thioglycoside tolylthio β-d-glucoside was also catalyzed. From a series of prepared analogues of 1 it was found that the catalysis was associated with the hydroxyl groups α to the nitril groups. The monocyanohydrin 6-C-cyano-β-cyclodextrin (3) was also found to catalyze the hydrolysis of 4-nitrophenyl β-glucopyranoside with

  （6 A R，6 D R）-6 A，6 D -Di- C-氰基-β-环糊精（1）和6 A，6 D -di- C-氰基-α-环糊精（2）合成并结果显示，其遵循米利斯-门腾动力学反应，可催化芳基糖苷水解为葡萄糖和苯酚。在pH8.0和4-硝基苯基α-D-吡喃葡萄糖苷的59℃水解物通过催化1与ķ中号= 10.5±1.5毫米，ķ猫= 1.42（±0.09）×10 - 4个小号- 1，和ķ猫/ ķ uncat = 7922.用的浓度观察到催化1低至10μM。包含糖部分和4-硝基-立体化学的变化的其他芳基糖苷的水解，2-硝基，2- aldehydo-，和2,4-二硝基还通过催化1和2与ķ猫/ ķ uncat范围为4至7100。还催化了苯基β- d-葡糖苷或硫代糖苷甲苯基硫代β- d-葡糖苷的水解。来自一系列准备好的类似物1发现该催化作用与腈基上的羟基α有关。所述monocyanohydrin 6- Ç氰
• Simple cyclodextrin aldehydes as excellent artificial oxidases
  作者：Thomas Hauch Fenger、Mikael Bols

  DOI：10.1007/s10847-010-9771-y

  日期：2011.4

  Cyclodextrin based oxidases, with a ketone as functional group are well known as good artificial enzyme mimics (Fenger et al. Org Biomol Chem 7:933–943; Marinescu and Bols Angew Chem Int Ed 45:4590–4593; Bjerre et al. Eur J Org Chem 704–710; Marinescu et al. J Am Chem Soc 127:17578–17579). We here report a series of modified cyclodextrins, having aldehydes as functional groups. The aldehyde based artificial enzymes have, in most cases, better catalysis than the ketones, because of their powerful covalent binding of hydrogen peroxide. Among the modified cyclodextrins studied are mono and di aldehydes on the 6 positions, with or without methylated hydroxyl groups. The aldehyde functionality was also introduced close to the secondary side, by attaching ethoxy-2-al or propoxy-3-al to the 2 position. The modified cyclodextrins showed excellent enzymatic activity towards oxidation of different aminophenols, and 4-methoxy benzyl alcohol with hydrogen peroxide as a stoichiometric oxidant. Rate enhancements up to 4,600 were achieved for oxidation of 4-methoxy benzyl alcohol, where as oxidation of amines gave rate enhancements up to 3,400. The artificial oxidases catalyses oxidations under enzymatic conditions (water, pH 7, 25 °C), following Michaelis–Menten kinetics. To confirm the enzyme activity, inhibition studies with sodium naphthalene-2-sulfonate were carried out. These studies showed competitive inhibition of the enzymes, verifying the cyclodextrins enzyme like character.

  众所周知，以酮为官能团的环糊精氧化酶是良好的人工酶模拟物（Fenger et al.Org Biomol Chem 7:933-943; Marinescu and Bols Angew Chem Int Ed 45:4590-4593; Bjerre et al.Eur J Org Chem 704-710; Marinescu et al.J Am Chem Soc 127:17578-17579）。我们在此报告了一系列以醛为官能团的改性环糊精。在大多数情况下，以醛为基础的人工酶比酮类具有更好的催化作用，因为它们能与过氧化氢产生强大的共价结合。在所研究的改性环糊精中，有 6 个位置上的单醛和二醛，有或没有甲基化羟基。此外，还通过在 2 位上连接乙氧基-2-al 或丙氧基-3-al，在靠近仲侧的位置引入了醛官能团。修饰后的环糊精对不同氨基苯酚和 4-甲氧基苯甲醇（以过氧化氢作为定量氧化剂）的氧化显示出卓越的酶活性。氧化 4-甲氧基苯甲醇的速率可提高到 4 600，而氧化胺的速率可提高到 3 400。人工氧化酶在酶促条件下（水、pH 值 7、25 °C），按照 Michaelis-Menten 动力学催化氧化。为了证实酶的活性，还用萘-2-磺酸钠进行了抑制研究。这些研究显示了对酶的竞争性抑制，验证了环糊精的酶类似特性。
• 5A,5D-dicarboxy-β-cyclodextrin derivatives - a route for regioselectively difunctionalized permethyl-β-cyclodextrin
  作者：Yasuhisa Kuroda、Osamu Kobayashi、Yasuhiko Suzuki、Hisanobu Ogoshi

  DOI：10.1016/s0040-4039(01)93941-3

  日期：1989.1
• A General Method for the Synthesis of Cyclodextrinyl Aldehydes and Carboxylic Acids
  作者：Juyoung Yoon、Sungyeap Hong、Kristy A. Martin、Anthony W. Czarnik

  DOI：10.1021/jo00114a030

  日期：1995.5

  The selective synthesis of the primary-side monoaldehyde of beta-cyclodextrin, 6-deoxy-6-formyl-beta-cyclodextrin, was accomplished by oxidation of the corresponding tosylate utilizing the Nace reaction (DMSO/collidine). This monoaldehyde was then used as the starting material in several reactions including reduction, addition of NaHSO3, addition of the alpha-nucleophiles hydroxylamine and hydrazine, and reductive amination. Of particular interest is the conversion of the monoaldehyde to the primary side carboxylic acid, 6-deoxy-6-carboxy-beta-cyclodextrin, via bromine oxidation. This general method sequence can be applied to any tosyl derivative of cyclodextrin as demonstrated in the synthesis of beta-cyclodextrin-A,D-dialdehyde and beta-cyclodextrin-A,D-diacid.