2,3,4,2',3',4'-hexa-O-acetyl-6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose | 162019-36-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,4,2',3',4'-hexa-O-acetyl-6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose
• 英文别名: [(2R,3R,4S,5R,6R)-4,5-diacetyloxy-2-(isothiocyanatomethyl)-6-[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-(isothiocyanatomethyl)oxan-2-yl]oxyoxan-3-yl] acetate
• CAS: 162019-36-5
• 化学式: C₂₆H₃₂N₂O₁₅S₂
• 分子量: 676.676
• InChiKey: OBWWSLYVTUIXNS-PCIRLDFKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  45
• 可旋转键数：
  18
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  274
• 氢给体数：
  0
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  2,3,4,2',3',4'-hexa-O-acetyl-6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose 在 吡啶 、 水 作用下， 反应 6.0h， 以43%的产率得到N,N'-bis-(2,3,4,2',3',4'-hexa-O-acetyl-6,6'-dideoxy-6'-isothiocyanato-α,α'-trehalos-6-yl)thiourea
  参考文献：
  名称：

  Synthesis, Structure, and Inclusion Capabilities of Trehalose-Based Cyclodextrin Analogues (Cyclotrehalans)

  摘要：

  Concise and efficient strategies toward the synthesis of D-2h- and D-3h-symmetric cyclodextrin analogues alternating alpha,alpha'-trehalose disaccharide subunits and pseudoamide segments (cyclotrehalans, CTs) are reported. The conformational properties of these cyclooligosaccharides are governed by the rigidity of the alpha,alpha'-trehalose disaccharide repeating unit and the partial double-bond character of the N-(C=X) linkages. In contrast to the typical concave-shaped cavity of cyclodextrins (CDs), CTs feature a convex-shaped hydrophobic cavity in which the beta-face of the monosaccharide subunits is oriented toward the inner side, as supported by NMR and modeling (molecular mechanics and dynamics) studies. In the case of cyclodimeric CTs (CT2s), the existence of intramolecular hydrogen bonds results in collapsed cavities, too small to allow the formation of inclusion complexes with organic molecules. Cyclotrimeric CTs (CT3s) display cavity sizes that are intermediate between those of alpha CD and beta CD, ideally suited for the complexation of complementary guests with ternary symmetry such as adamantane 1-carboxylate (AC). The higher flexibility of the pseudoamide bridges as compared with classical glycosidic linkages endow these glyconanocavities with some conformational adaptability properties, making them better suited than CDs for complexation of angular guests, as seen from comparative inclusion capability experiments against the fluorescent probes 6-p-toluidinonaphthalene-2-sulfonate (TNS; linear) and 8-anilinonaphthalene-1-sulfonate (ANS; angular).

  DOI：

  10.1021/jo800048s
• 作为产物：
  描述：

  2,2',3,3',4,4'-hexa-O-acetyl-6,6'-diamino-6,6'-deoxy-α,α'-trehalose 、 硫光气 在 calcium carbonate 作用下， 以 水 、 丙酮 为溶剂， 生成 2,3,4,2',3',4'-hexa-O-acetyl-6,6'-dideoxy-6,6'-diisothiocyanato-α,α'-trehalose
  参考文献：
  名称：

  Synthesis, conformational flexibility and preliminary complexation behaviour of α,α′-trehalose-based macrocycles containing thiourea spacers

  摘要：

  报告了一种高效合成大环配体的方法，该配体包含两个δ,δâ²-三卤糖亚基，通过 1,3-thiourea 间隔物在主 C-6,6â²位置连接；NâC(S) 键的 Z/E 构型受分子内氢键和立体因素的影响。

  DOI：

  10.1039/c39950000057

文献信息

• One-step synthesis of non-anomeric sugar isothiocyanates from sugar azides
  作者：M.Isabel Garcı́a-Moreno、Paula Dı́az-Pérez、Juan M. Benito、Carmen Ortiz Mellet、Jacques Defaye、José M. Garcı́a Fernández

  DOI：10.1016/s0008-6215(02)00273-2

  日期：2002.11

  yield. No products arising from O --> N acyl migration or formation of dimeric carbodiimides were observed. Interestingly, a polymer-supported triarylphosphine can advantageously replace triphenylphosphine, thus limiting the purification step to a simple filtration process. The reaction also allows the preparation of 5-deoxy-5-isothiocyanato sugars, a hitherto unknown class of compounds, from the corresponding

  初级叠氮基脱氧糖与三苯基膦-二硫化碳的串联Staudinger-aza-Wittig反应以高收率提供了相应的初级脱氧异硫氰酸氰基糖。没有观察到由于O-> N酰基迁移或形成二聚碳二亚胺而产生的产物。有趣的是，聚合物负载的三芳基膦可以有利地代替三苯基膦，因此将纯化步骤限制为简单的过滤过程。该反应还允许从相应的叠氮化物前体制备5-脱氧-5-异硫氰酸根合糖，这是迄今未知的一类化合物。在这些反应条件下，在内环碳原子上带有叠氮基的仲糖叠氮化物提供了低得多的异硫氰化产率。
• Cyclotrehalins: Cyclooligosaccharide Receptors Featuring a Hydrophobic Cavity
  作者：Juan M. Benito、José L. Jiménez Blanco、C. Ortiz Mellet、José M. García Fernández

  DOI：10.1002/1521-3773(20021004)41:19<3674::aid-anie3674>3.0.co;2-f

  日期：2002.10.4
• Size-Tunable Trehalose-Based Nanocavities: Synthesis, Structure, and Inclusion Properties of Large-Ring Cyclotrehalans
  作者：David Rodríguez-Lucena、Carmen Ortiz Mellet、Carlos Jaime、Kepa K. Burusco、José M. García Fernández、Juan M. Benito

  DOI：10.1021/jo802796p

  日期：2009.4.17

  [GRAPHICS]An efficient strategy toward the synthesis of large-ring cyclodextrin (CD) analogs alternating alpha,alpha'-trehalose disaccharide subunits and pseudoamide segments (cyclotrehalans, CTs), involving a bimolecular macrocyclization reaction as the key step, is reported. NMR and molecular modeling confirmed that the eight and ten alpha-D-glucopyranoside subunits in tetrameric and pentameric CT homologues (CT4 and CT5, respectively) are magnetically equivalent, as in the gamma and epsilon CD counterparts. Yet, the orientation of the monosaccharide constituents is reversed in CTs as compared with CDs, the beta-face being directed to the inside of the nanometric cavity while the alpha-face remains in contact with the bulk solvent. Molecular mechanics and dynamics experiments revealed that the cyclooligosaccharide architecture in CT4 and CT5 is relatively flexible, which is in contrast to that previously observed for the first members of the CT series (CT2 and CT3 oligomers). Thus, although in their fully expanded conformation their cavity size is close to that of gamma CD, the higher mobility of the pseudoamide bridges as compared with classical glycosidic linkages endows these hosts with induced fitting capabilities toward smaller guests.