(2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(pent-4-en-1-yloxy)tetrahydro-2H-pyran | 113548-09-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(pent-4-en-1-yloxy)tetrahydro-2H-pyran
• 英文别名: n-pent-4-enyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside；pent-4-enyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside；pentenyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside；(2S,3R,4S,5R,6R)-2-pent-4-enoxy-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxane
• CAS: 113548-09-7
• 化学式: C₃₉H₄₄O₆
• 分子量: 608.775
• InChiKey: UJKZBFGKKCLGDY-QGVRFUEOSA-N

物化性质

• 沸点：
  696.8±55.0 °C(predicted)
• 密度：
  1.15±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  45
• 可旋转键数：
  18
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(pent-4-en-1-yloxy)tetrahydro-2H-pyran 在 palladium on activated charcoal sodium periodate 、 四氧化锇 、 ammonium formate 、 三乙酰氧基硼氢化钠 、 N-甲基吗啉氧化物 作用下， 以 四氢呋喃 、 甲醇 、 1,2-二氯乙烷 为溶剂， 反应 63.0h， 生成 2-(N-(4-(α-D-glucopyranosyloxy)butyl)amino)benzamide
  参考文献：
  名称：

  Fluorescence labelling of carbohydrates with 2-aminobenzamide (2AB)

  摘要：

  2-Aminobenzamide (2AB) is a common fluorescence label attached to reducing oligosaccharides by a reductive amination procedure. Chemical investigation of the published literature procedure reveals labelling occurs by the expected mechanism for both protected and unprotected glucose derivatives to yield open-chain carbohydrates rather than result in the formation of any heterocyclic materials. Pentenyl glucosides may also be readily attached to the 2AB label by a sequence of dihydroxylation, periodate cleavage and subsequent reductive amination of the resulting aldehyde. :,AB labelling is compatible with deprotection of both acetate and benzyl protecting groups. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00477-8
• 作为产物：
  描述：

  pent-4-enyl D-glucopyranoside 在 吡啶 、 sodium hydride 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (2R,3R,4S,5R,6S)-3,4,5-tris(benzyloxy)-2-((benzyloxy)methyl)-6-(pent-4-en-1-yloxy)tetrahydro-2H-pyran
  参考文献：
  名称：

  A Solvation-Assisted Model for Estimating Anomeric Reactivity. Predicted versus Observed Trends in Hydrolysis of n-Pentenyl Glycosides¹

  摘要：

  An attempt has been made to predict qualitative trends in reactivity at the anomeric center, using N-bromosuccinimide-induced hydrolysis of n-pentenyl glycosides (NPGs) as the experimental model. Calculated relative activation energies based on internal energy differences between a reactant and the associated intermediate are not always in agreement with experimental observations. However, solvation energies obtained by the generalized Born surface area model in MacroModel developed by Still et al. give modified activation energies that are in excellent agreement with the experimentally observed trends. It is shown that the solvation model does not disturb the normally observed reactivity trends that can be rationalized on the basis of internal energies alone. The value of the methodology has been demonstrated for several substrates by first-calculating their relative activation energies, then testing them experimentally, and finding excellent agreement with predictions.

  DOI：

  10.1021/jo9601223

文献信息

• Cooperative Catalysis in Glycosidation Reactions with<i>O</i>-Glycosyl Trichloroacetimidates as Glycosyl Donors
  作者：Yiqun Geng、Amit Kumar、Hassan M. Faidallah、Hassan A. Albar、Ibrahim A. Mhkalid、Richard R. Schmidt

  DOI：10.1002/anie.201302158

  日期：2013.9.16

  Thiourea mediates cooperative glycosidation through hydrogen bonding. N,N′‐Diarylthiourea as cocatalyst enforces an SN2‐type acid‐catalyzed glycosidation even at room temperature (see scheme; Bn=benzyl). From O‐(α‐glycosyl) trichloroacetimidates as glycosyl donors and various acceptors, β‐glycosides are preferentially or exclusively obtained.

  硫脲通过氢键介导协同糖基化。N，N'-二芳基硫脲作为助催化剂即使在室温下也可增强S N 2型酸催化的糖苷化作用（见方案； Bn =苄基）。从O-（α-糖基）三氯乙酰亚氨酸盐作为糖基供体和各种受体，可以优先或仅从中获得β-糖苷。
• Gold(III) Chloride and Phenylacetylene: A Catalyst System for the Ferrier Rearrangement, and<i>O</i>-Glycosylation of 1-<i>O</i>-Acetyl Sugars as Glycosyl Donors
  作者：Rashmi Roy、Parasuraman Rajasekaran、Asadulla Mallick、Yashwant D. Vankar

  DOI：10.1002/ejoc.201402606

  日期：2014.9

  have developed a new catalyst system comprising AuCl3 and phenylacetylene that promotes the Ferrier rearrangement of glycals and 2-acetoxymethylglycals with different nucleophiles, and also the O-glycosylation of 1-O-acetyl sugars to obtain a variety of useful glycosides at room temperature through relay catalysis. Good anomeric selectivity was observed for the Ferrier rearrangements, whereas the O-glycosylation

  我们开发了一种新的催化剂体系，包含 AuCl3 和苯乙炔，可促进具有不同亲核试剂的糖类和 2-乙酰氧基甲基糖类的费里尔重排，以及 1-O-乙酰糖的 O-糖基化，以通过以下方式在室温下获得各种有用的糖苷中继催化。对于 Ferrier 重排观察到良好的异头异构体选择性，而 1-O-乙酰糖的 O-糖基化产生具有中等至极好选择性的非对映异构体混合物。
• Direct elaboration of pent-4-enyl glycosides into disaccharides
  作者：Bert Fraser-Reid、Peter Konradsson、David R. Mootoo、Uko Udodong

  DOI：10.1039/c39880000823

  日期：——

  Pent-4-enyl glycosides, on treatment with halonium ions, become chemospecifically activated so that coupling with partially protected monosaccharides can be effected, leading to the in situ formation of disaccharides.

  Pent-4-enyl糖苷在用lon离子处理后被化学特异性活化，因此可以与部分受保护的单糖偶联，从而导致二糖的原位形成。
• AuCl3-AgOTf promoted O-glycosylation using anomeric sulfoxides as glycosyl donors at room temperature
  作者：Ashokkumar Palanivel、Ande Chennaiah、Sateesh Dubbu、Asadulla Mallick、Yashwant D. Vankar

  DOI：10.1016/j.carres.2016.11.012

  日期：2017.1

  glycosyl donors using AuCl3/AgOTf reagent system has been described. Under optimal reaction conditions, both armed and disarmed glycosyl sulfoxide donors were found to react with a range of primary, secondary, and tertiary alcohol acceptors, and sugar derived glycosyl acceptors to afford the corresponding glycosides in moderate to good yields with predictable selectivity. The reactions are quick (20-60 min)

  已经描述了使用AuCl3 / AgOTf试剂系统将亚砜活化为糖基供体。在最佳反应条件下，发现武装和解除武装的糖基亚砜供体都与一定范围的伯，仲和叔醇受体和糖衍生的糖基受体反应，以中等到良好的产率提供了可预测的选择性的相应糖苷。反应快速（20-60分钟），在室温下容易进行，并且反应条件可耐受酸敏感性基团。
• Glycosyl fluorides from <i>n</i>-pentenyl-related glycosyl donors — Application to glycosylation strategies
  作者：Bert Fraser-Reid、J. Cristobal Lopez、Paloma Bernal-Albert、Ana M. Gomez、Clara Uriel、Juan Ventura

  DOI：10.1139/cjc-2012-0285

  日期：2013.1

  fluorides by a variety of methods. In the case of NPGs, Barluenga’s reagent, bis(pyridinium)iodonium(I)tetrafluoroborate (IPy2BF4), gives good yields of glycosyl fluorides when HF–pyridine complex is used as an additional fluoride source. NPOEs can be activated either by a combination of electrophilic iodonium (Barluenga’s reagent) and HBF4 or by the action of HF–pyridine complex. The ensuing glycosyl

  正戊烯基糖苷 (NPG) 和正戊烯基原酸酯 (NPOE) 已通过多种方法转化为糖基氟。在 NPG 的情况下，当使用 HF-吡啶复合物作为额外的氟化物来源时，Barluenga 试剂双（吡啶鎓）碘鎓（I）四氟硼酸盐（IPy2BF4）可产生良好的糖基氟化物产率。NPOE 可以通过亲电子碘鎓（Barluenga 试剂）和 HBF4 的组合或通过 HF-吡啶复合物的作用被激活。当遇到 NPG 时，随之而来的糖基氟化物会形成一对半正交的糖基供体。