2(A-F),3(A-F),6(B,C,E,F)-hexadeca-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: 2(A-F),3(A-F),6(B,C,E,F)-hexadeca-O-benzyl-α-cyclodextrin
• 英文别名: 2^A-F,3^A-F,6^C-D,E-F-hexadeca-O-benzyl-α-cyclodextrin；6(B),6(C),6(E),6(F)-tetra-O-benzyl-2,3-di-O-benzyl-α-cyclodextrin；2(A-F),3(A-F),6(B),6(C),6(E),6(F)-hexadecakis-O-benzyl-α-cyclodextrin；2(I), 2(II), 2(III), 2(IV), 2(V), 2(VI), 3(I), 3(II), 3(III), 3(IV), 3(V), 3(VI), 6(II), 6(III), 6(V),6(VI)-hexadeca-O-benzyl-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)-20-(hydroxymethyl)-31,32,33,34,35,36,37,38,39,40,41,42-dodecakis(phenylmethoxy)-10,15,25,30-tetrakis(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]dotetracontan-5-yl]methanol
• 化学式: C₁₄₈H₁₅₆O₃₀
• 分子量: 2414.85
• InChiKey: MSPUPKXGCJVFMN-WVJPFMMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  19.6
• 重原子数：
  178
• 可旋转键数：
  54
• 环数：
  24.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  299
• 氢给体数：
  2
• 氢受体数：
  30

反应信息

• 作为反应物：
  描述：

  2(A-F),3(A-F),6(B,C,E,F)-hexadeca-O-benzyl-α-cyclodextrin 在 甲基磺酰氯 、 三乙胺 、 咪唑 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 以90%的产率得到6^A,6^D-dideoxy-6^A,6^D-dichloro-2^A-F,3^A-F,6^B,6^C,6^E,6^F-hexadeca-O-benzyl-α-cyclodextrin
  参考文献：
  名称：

  α-环糊精上完全相反的卡宾：有机金属配合物的合成、表征和乙醇和水中的 Suzuki-Miyaura 偶联

  摘要：

  两个基于卡宾的配体已连接到全苄基化和全甲基化环糊精。他们的钯配合物被合成、表征并用作乙醇和水中铃木-宫浦偶联反应的催化剂。

  DOI：

  10.1002/ejoc.201300190
• 作为产物：
  描述：

  hexakis-(2,3,6-tri-O-benzyl)-α-cyclodextrin 在 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以82%的产率得到2(A-F),3(A-F),6(B,C,E,F)-hexadeca-O-benzyl-α-cyclodextrin
  参考文献：
  名称：

  pH 响应性选择性官能化环糊精对假轮烷脱螺纹的精确速率控制

  摘要：

  一组用零、一、二或六种胺官能化的环糊精被证明可以根据 pH 值及其取代模式控制它们在分子轴上的穿线和脱线速度。该系统的独创性在于通过直接在大周期上操作刺激来控制开关的速率。

  DOI：

  10.1021/acs.orglett.1c02940

文献信息

• Cavitand supported tetraphosphine: cyclodextrin offers a useful platform for Suzuki-Miyaura cross-coupling
  作者：Elena Zaborova、Julia Deschamp、Samuel Guieu、Yves Blériot、Giovanni Poli、Mickaël Ménand、David Madec、Guillaume Prestat、Matthieu Sollogoub

  DOI：10.1039/c1cc12241j

  日期：——

  The cyclodextrin-tetraphosphine hybrid coined α-Cytep allows turnover numbers up to 340 000 000 000 and turnover frequencies up to 1 000 000 000 h−1 to be reached in Suzuki–Miyaura reactions. These exceptional figures are clearly linked to the outstanding longevity of the reactive species induced by the ligand α-Cytep and illustrates the rising potential of cyclodextrins in catalytic applications.

  名为α-Cytep的环糊精-四膦杂化物在铃木-宫浦反应中达到了高达340万亿的周转数和高达10亿小时⁻¹的周转频率。这些卓越的数据显然与α-Cytep配体引发的活性物种的非凡寿命有关，并展示了环糊精在催化应用中日益增长的潜力。
• Cyclodextrin derivatives with cyanohydrin and carboxylate groups as artificial glycosidases
  作者：Fernando Ortega-Caballero、Mikael Bols

  DOI：10.1139/v06-039

  日期：2006.4.1

  Two cyclodextrin derivatives (1 and 2) were prepared in an attempt to create glycosidase mimics with a general acid catalyst and a nucleophilic carboxylate group. The catalysts 1 and 2 were found to catalyse the hydrolysis of 4-nitrophenyl β-D-glucopyranoside at pH 8.0, but rapidly underwent decomposition with loss of hydrogen cyanide to convert the cyanohydrin to the corresponding aldehyde. The initial rate of the catalysis shows that the cyanohydrin group in these molecules functions as a good catalyst, but that the carboxylate has no positive effect. The decomposition product aldehydes display little or no catalysis. A mechanism for the decomposition is suggested.Key words: biomimicry, enzyme model, kinetics, intramolecular reaction.

  我们制备了两种环糊精衍生物（1 和 2），试图利用一般酸催化剂和亲核羧酸基来制造糖苷酶模拟物。研究发现，催化剂 1 和 2 在 pH 值为 8.0 时可催化 4-硝基苯基 β-D-Glucopyranoside 的水解，但随着氰化氢的流失，氰醇迅速分解为相应的醛。催化的初始速率表明，这些分子中的氰醇基起到了很好的催化作用，而羧酸盐则没有积极作用。分解产物醛几乎没有催化作用。关键词：生物模拟、酶模型、动力学、分子内反应。
• 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。
• Cyclodextrin ketones as oxidation catalysts: Investigation of bridged derivatives
  作者：Thomas Hauch Fenger、Lavinia G. Marinescu、Mikael Bols

  DOI：10.1039/b814245a

  日期：——

  α-cyclodextrin derivatives containing a 3, 4 or 5 membered ether-linked bridge between the 6A and 6D oxygen atoms, with and without a ketone, were prepared. The synthesis used perbenzylated α-cyclodextrin A,D-diol as a starting material upon which O-alkylation and further modifications led to the di-O-(buta-1,4-diyl), the di-O-(penta-1,5-diyl) and the di-O-(buta-2-on-1,4-diyl) derivatives, which were

  制备了一系列α-环糊精衍生物，其在6A和6D氧原子之间包含3、4或5元醚连接的桥，带有或不带有酮。合成过程中使用过苄基化的α-环糊精A，D-二醇作为原料，在该原料上进行O-烷基化和进一步的修饰，生成二-O-（buta-1,4-diyl），二-O-（penta-1） ，5-二基）和二-O-（buta-2-on-1,4-diyl）衍生物，它们被去苄基化，并与先前报道的di-O-（propa-2-on-1,3 -二基）衍生物。还制备了二-O-（丙-2-on-1,3-二基）的全甲基化衍生物和buta-1,4-二基衍生物。6A，6D-二-O-（丙-2-on-1,3-二基）-6C，6F-二-O-甲基和二-O还制备了新戊酰基衍生物。分析了新化合物对胺和醇氧化的催化作用。