[(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36S,37R,38S,39R,40S,41R,42S,43R,44S,45R,46S,47R,48S,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecamethoxy-5,15,20,25,30,35-hexakis(methoxymethyl)-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-10-yl]methyl 4-methylbenzenesulfonate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36S,37R,38S,39R,40S,41R,42S,43R,44S,45R,46S,47R,48S,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecamethoxy-5,15,20,25,30,35-hexakis(methoxymethyl)-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-10-yl]methyl 4-methylbenzenesulfonate
• 化学式: C₆₉H₁₁₆O₃₇S
• 分子量: 1569.72
• InChiKey: DOOVJVNNYILSHY-SGJXESGHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.3
• 重原子数：
  107
• 可旋转键数：
  30
• 环数：
  22.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  366
• 氢给体数：
  0
• 氢受体数：
  37

反应信息

• 作为反应物：
  描述：

  [(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36S,37R,38S,39R,40S,41R,42S,43R,44S,45R,46S,47R,48S,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecamethoxy-5,15,20,25,30,35-hexakis(methoxymethyl)-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-10-yl]methyl 4-methylbenzenesulfonate 在 萘 、 sodium 作用下， 以 四氢呋喃 为溶剂， 以76%的产率得到permethylated mono-6-hydroxy-β-cyclodextrin
  参考文献：
  名称：

  多功能 6-O-单糖基和 6-单羟基全​​甲基化 α-、β- 和 γ-环糊精的新大规模制备

  摘要：

  描述了用于制备通用 6-O-单糖基和 6-单羟基全​​甲基化 α-、β-和 γ-环糊精的新实用方法。

  DOI：

  10.1246/cl.2002.514
• 作为产物：
  描述：

  Mono-6-O-(p-toluenesulfonyl)-beta-cyclodextrin 、 硫酸二甲酯 在 sodium hydroxide 作用下， 以 水 、 四氢呋喃 为溶剂， 反应 0.17h， 以57%的产率得到[(1R,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31R,33R,35R,36S,37R,38S,39R,40S,41R,42S,43R,44S,45R,46S,47R,48S,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecamethoxy-5,15,20,25,30,35-hexakis(methoxymethyl)-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-10-yl]methyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  碱定向钯催化的丙烯醛乙缩醛在水中的Heck芳基化。

  摘要：

  描述了在存在RAME-β-CD的水中作为溶剂的[Pd（NH 3）4 ] Cl 2催化的丙烯醛乙缩醛的选择性Heck芳基化。取决于对肉桂醛2或3-芳基丙酸酯1分别具有良好至高选择性的碱（即NaOAc或HN（i- Pr）2）。结果支持了根据碱形成了不同的钯中间体配合物。使用NaOAc，优先生成{[ArPdX（H 2 O）2 ]}复合物，得到肉桂醛2。另一方面，在HN（i -Pr）存在下如图2所示，将产生L型配体[ArPdX（HN（i -Pr ）2（H 2 O）]或[ArPdX（HN（i -Pr ）2（HN（i -Pr）2））]，从而导致在形成3-芳基丙酸酯的1。在过去，协调胺参与很可能是通过分子内形成酯的顺式β-H的消除。

  DOI：

  10.1016/j.apcata.2013.10.004

文献信息

• Synthesis, Rhodium Complexes and Catalytic Applications of a New Water-Soluble Triphenylphosphane-Modified β-Cyclodextrin
  作者：François-Xavier Legrand、Natacha Six、Christian Slomianny、Hervé Bricout、Sébastien Tilloy、Eric Monflier

  DOI：10.1002/adsc.201000917

  日期：2011.5

  of inclusion complexes. Associated to a rhodium precursor, PM‐β‐CD‐OTPP is able to generate soluble rhodium species in water. In addition, NMR experiments showed that the cyclodextrin cavity remains accessible for a guest even when PM‐β‐CD‐OTPP is coordinated to rhodium. Finally, this ligand was efficient for rhodium‐catalyzed hydrogenation and hydroformylation performed in aqueous medium.

  合成了一种基于β-环糊精骨架的新三苯基膦（PM-β-CD-OTPP）。可以通过使用纳米沉淀法将该配体分散在水中。透射电子显微镜和NMR光谱表明PM-β-CD-OTPP聚集在水中并形成稳定的分散体。在存在选定的水溶性客体的情况下，通过形成包合物可以显着提高其水溶性。与铑前体有关，PM-β-CD-OTPP能够在水中生成可溶性铑。此外，NMR实验表明，即使PM-β-CD-OTPP与铑配位，客人仍可进入环糊精腔。最后，该配体对于在水性介质中进行铑催化的加氢和加氢甲酰化反应非常有效。
• Preparation and Photodynamic Activities of Silicon(IV) Phthalocyanines Substituted with Permethylated β-Cyclodextrins
  作者：Janet T. F. Lau、Pui-Chi Lo、Wing-Ping Fong、Dennis K. P. Ng

  DOI：10.1002/chem.201100621

  日期：2011.6.27

  A series of silicon(IV) phthalocyanines linked to two permethylated β‐cyclodextrin moieties through different spacers at the axial positions have been synthesized and characterized. The effects of these spacers on the photophysical properties and in vitro photodynamic activities have also been examined. Having two bulky hydrophilic substituents, all of these compounds are soluble and essentially nonaggregated

  合成并表征了一系列通过两个不同间隔基与两个全甲基化β-环糊精部分连接的硅（IV）酞菁。还检查了这些间隔物对光物理性质和体外光动力活性的影响。具有两个庞大的亲水性取代基，所有这些化合物都可溶于DMF，甚至在水性介质中且基本上不聚集。对于类似物而言，DMF中的荧光和单态氧量子产率较低，间隔基中的氨基与酞菁环之间的间隔最短。该化合物的荧光量子产率在水中可能由于氨基的质子化而增加，这抑制了还原淬灭过程。50个值在0.04-1.32μ的范围中号。具有α，ω-氨基羟基戊基接头的类似物显示出最高的效价，这可以归因于其高细胞摄取和高效产生细胞内活性氧的能力。该化合物还在溶酶体中显示优先定位，主要通过凋亡诱导细胞死亡，并在体内抑制肿瘤的生长。结果表明，它是用于光动力疗法的有前途的光敏剂。
• Entropy-Controlled Supramolecular Photochirogenesis:  Enantiodifferentiating <i>Z</i><i>−</i><i>E</i> Photoisomerization of Cyclooctene Included and Sensitized by Permethylated 6-<i>O</i>-Modified β-Cyclodextrins
  作者：Gaku Fukuhara、Tadashi Mori、Takehiko Wada、Yoshihisa Inoue

  DOI：10.1021/jo061389x

  日期：2006.10.1

  = −51.1 J mol-1 K-1). Upon supramolecular photosensitization with 2a−2d, 1Z isomerized to the (E)-isomer (1E) in moderate enantiomeric excesses (ee's), which however displayed significant temperature dependence with accompanying switching of the product's chirality in an extreme case. Such dynamic behavior of ee is very different from that reported for the photosensitization with nonmethylated cyclodextrin

  合成了全甲基化的6 - O-修饰的β-环糊精2a - 2d作为具有柔性骨架的新型光敏宿主。苯甲酸酯2a的圆二色性（CD）和2D NMR光谱检查表明，苯甲酸酯部分已深深地包含在水溶液中的自身腔中。在25°C下，将（Z）-环辛烯（1Z）添加到50％的2a甲醇水溶液中时，如CD光谱变化所示，2a的苯甲酸酯部分逐渐从腔中排除。约伯的阴谋揭示了2a与1Z的1：1络合物的形成。用于络合的结合常数1Z由图2a，通过CD光谱滴定在50％含水甲醇中，在各种温度下测定。对获得的数据进行的范霍夫分析提供了热力学参数（ΔH °= -3.1 kJ mol - 1，ΔS °= 48.5 J mol - 1 K - 1），证明了全甲基化环糊精的熵驱动络合。这与由焓驱动的非甲基化的β-环糊精苯甲酸的1Z络合物形成鲜明对比（ΔH °= -31.8 kJ mol - 1和ΔS°= −51.1 J mol - 1 K - 1）。通过2a
• A manganese porphyrin–α-cyclodextrin conjugate as an artificial enzyme for the catalytic epoxidation of polybutadiene
  作者：Qi-Wei Zhang、Johannes A. A. W. Elemans、Paul B. White、Roeland J. M. Nolte

  DOI：10.1039/c8cc02320d

  日期：——

  manganese porphyrin–α-cyclodextrin conjugate as a catalyst for the epoxidation of cis-polybutadiene with trans-epoxide preference, which is a reverse stereoselectivity as compared to normal porphyrin catalysts. A clamp-like mechanism is proposed based on a combination of circular dichroism analysis, molecular modeling, and a series of epoxidation experiments.

  我们将锰卟啉-α-环糊精偶联物描述为顺式-聚丁二烯与反式环氧化物优先环氧化的催化剂，与普通的卟啉催化剂相比，这是反向的立体选择性。结合圆二色性分析，分子建模和一系列环氧化实验，提出了一种钳状机制。
• Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin
  作者：Jun Terao、Yohei Konoshima、Akitoshi Matono、Hiroshi Masai、Tetsuaki Fujihara、Yasushi Tsuji

  DOI：10.3762/bjoc.10.297

  日期：——

  We synthesized symmetrically insulated oligo(para-phenylene) and oligothiophene with a pseudo-linked [3]rotaxane structure by full rotation of glucopyranose units via a flipping (tumbling) mechanism in the π-conjugated guest having two permethylated β-cyclodextrin units at both ends. We also succeeded in the synthesis of an organic-soluble fixed [3]rotaxane by a cross-coupling or complexation reaction of thus formed pseudo linked [3]rotaxane. Oligo(para-phenylene), oligothiophene, and porphyrin derivatives were used as π-conjugated guests with stopper groups.

  我们通过在π共轭客体中具有两个双甲基化β-环糊精单元的两端全旋转葡萄糖吡喃单元的翻转（翻滚）机制，合成了具有伪链接[3]轮烷结构的对称绝缘寡聚（对）苯和寡噻吩。我们还通过交叉偶联或络合反应成功合成了有机溶剂可溶的固定[3]轮烷。寡（对）苯、寡噻吩和卟啉衍生物被用作带有停滞基团的π共轭客体。