Pent-4-enyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside | 128503-35-5

• 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: Pent-4-enyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside
• 英文别名: 4-pentenyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside；[(2R,3R,4S,5R,6S)-3,4,5-triacetyloxy-6-pent-4-enoxyoxan-2-yl]methyl acetate
• CAS: 128503-35-5
• 化学式: C₁₉H₂₈O₁₀
• 分子量: 416.425
• InChiKey: RUZLEKUIXNODKZ-FQBWVUSXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  29
• 可旋转键数：
  14
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  Pent-4-enyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside 在 4-甲基苯磺酸吡啶 、 potassium carbonate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 Pent-4-enyl 4,6-O-benzylidene-α-D-glucopyranoside
  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
• 作为产物：
  描述：

  D-葡萄糖 在 吡啶 、 camphor-10-sulfonic acid 作用下， 反应 72.0h， 生成 Pent-4-enyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside
  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

• Iodonium ion generated in situ from N-iodosuccinimide and trifluoromethanesulphonic acid promotes direct linkage of ‘disarmed’ pent-4-enyl glycosides
  作者：Peter Konradsson、David R. Mootoo、Robert E. McDevitt、Bert Fraser-Reid

  DOI：10.1039/c39900000270

  日期：——

  N-Iodosuccinimide and trifluoromethanesulphonic acid provide a powerful source of Iodonium ion which allows ‘disarmed’ pent-4-enyl glycosides that normally respond sluggishly to lodonium dicollidine perchlorate, to react rapidly and to exhibit stereodirection via neighbouring group participation of C-2 esters.

  N-碘代琥珀酰亚胺和三氟甲磺酸提供了强大的碘离子源，它使通常通常对慢二氯可乐定高氯酸钾反应迟钝的“脱甲”戊-4-烯基糖苷反应迅速，并通过C-2酯的相邻基团参与而表现出立体定向性。
• Efficient glycosylation of unprotected sugars using sulfamic acid: A mild eco-friendly catalyst
  作者：Goutam Guchhait、Anup Kumar Misra

  DOI：10.1016/j.catcom.2011.07.016

  日期：2011.10

  Sulfamic acid, a mild and environmentally benign catalyst has been successfully used in the Fischer glycosylation of unprotected sugars for the preparation alkyl glycosides. A diverse range of aliphatic alcohols have been used to prepare a series of alkyl glycosides in good to excellent yield. (C) 2011 Elsevier B.V. All rights reserved.
• n-Pentenyl Glycoside Based Methodology for Determining the Relative Reactivities of Variously Protected Pairs of Glycosides
  作者：Bruce G. Wilson、Bert Fraser-Reid

  DOI：10.1021/jo00107a008

  日期：1995.1

  The relative rate of hydrolysis of an alpha/beta anomeric pair of glycosides is generally considered to provide insight into various factors that influence anomeric reactivity. However the fact that such hydrolyses are usually carried out with aqueous acids severely limits the range of substrates that can studied. This limitation is overcome with n-pentenyl glycosides (NPGs) which are hydrolyzed under neutral, oxidative conditions. A procedure is described in which a pair (e.g. alpha(1)/beta(1), alpha(1)/beta(2), beta(1)/beta(2), etc.) of NPGs is made to compete for an insufficient amount of N-bromosuccinimide, the relative rates of reaction being determined from HPLC peak heights of the unreacted starting materials. Some commonly used acid labile protecting groups, e.g. cyclic acetals and acetyl, are shown to exert profound effects upon relative and absolute rates of anomeric activation.
• Konstantinović; Predojević; Gojković, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2003, vol. 42, # 3, p. 666 - 669
  作者：Konstantinović、Predojević、Gojković、Pavlović

  DOI：——

  日期：——
• Fluorescence labelling of carbohydrates with 2-aminobenzamide (2AB)
  作者：Robert R. France、Ian Cumpstey、Terry D. Butters、Antony J. Fairbanks、Mark R. Wormald

  DOI：10.1016/s0957-4166(00)00477-8

  日期：2000.12

  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.