pent-4-enyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside | 50256-33-2

• 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-β-D-glucopyranoside
• 英文别名: n-pent-4-enyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside；4-pentenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside；4-Penten-1-yl 2,3,4,6-tetra-O-acetyl-b-D-glucopyranoside；[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-pent-4-enoxyoxan-2-yl]methyl acetate
• CAS: 50256-33-2
• 化学式: C₁₉H₂₈O₁₀
• 分子量: 416.425
• InChiKey: RUZLEKUIXNODKZ-UJWQCDCRSA-N

物化性质

• 熔点：
  45-46 °C(Solv: isopropyl ether (108-20-3))
• 沸点：
  463.6±45.0 °C(Predicted)
• 密度：
  1.20±0.1 g/cm3(Predicted)

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-β-D-glucopyranoside 在 sodium hydroxide 、 4 A molecular sieve 、 4-甲基苯磺酸吡啶 、 sodium cyanoborohydride 、 potassium carbonate 、 tetra-n-butylammonium hydrogen sulfate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 56.0h， 生成 pent-4-enyl 2,6-di-O-benzyl-β-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-β-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

• Solvent-free mechanochemical glycosylation in ball mill
  作者：Mohit Tyagi、Darpan Khurana、K.P. Ravindranathan Kartha

  DOI：10.1016/j.carres.2013.06.018

  日期：2013.9

  Starting from acetobromosugars and an alcohol (alkyl/substituted alkyl/akenyl/alkynyl/glyceryl/cyclohexyl/steryl) various O-glycosides have been prepared mechanochemically under solvent-free conditions employing a planetary ball mill in the presence of metal carbonates (environmentally benign or otherwise) as promoters. The method was proven to be mild and efficient and applicable on preparative scale for

  从乙溴糖和醇（烷基/取代的烷基/烯基/炔基/甘油基/环己基/硬脂基）开始，在无溶剂条件下，采用行星式球磨机，在金属碳酸盐存在下，通过机械化学方法制备了各种O-糖苷（环境上为良性或良性）。否则）作为发起人。该方法被证明是温和有效的，可用于制备规模的合成各种单糖和二糖苷的方法。这样产生的4-戊烯基糖苷可以在同一罐中连续四个反应中，以高分离产率转化为三唑取代的戊基糖苷，可以在药物化学领域中找到应用。
• BiBr₃-Promoted Activation of Peracetylated Glycosyl Iodides: Straightforward Access to Synthetically Useful 2-<i>O</i>-Deprotected Allyl Glycosides
  作者：Antonello Pastore、Matteo Adinolfi、Alfonso Iadonisi

  DOI：10.1002/ejoc.200800914

  日期：2008.12

  anomeric activation of acetylated glycosyl iodides. This reactivity can be exploited for straightforward access to allyl glycosides unprotected at the O-2 position. The reported protocol appears to be convenient in comparison with the pre-existing ones in that shorter experimental times are needed and the use of strong acids is avoided. Suitable structural features of substrates (6-deoxy sugars or use

  亚化学计量量的 BiBr3 能够促进乙酰化糖基碘的异头活化。这种反应性可用于直接获得在 O-2 位置未受保护的烯丙基糖苷。与先前存在的协议相比，报告的协议似乎很方便，因为需要更短的实验时间并且避免使用强酸。底物的合适结构特征（6-脱氧糖或使用苯甲酰基或甲氧基羰基 2-O 参与基团）将过程切换到优先糖苷化，而不会在 O-2 位置脱保护。（© Wiley-VCH Verlag GmbH & Co. KGaA , 69451 德国魏因海姆, 2008)
• The Asymmetric Dihydroxylation of Some Alkenyl b-D-Glucopyranosides: the Preparation of an Optically Pure Episulfide
  作者：Lorenzo M. Peci,、Robert V. Stick,、D. Matthew G. Tilbrook、Merilyn L. Winslade

  DOI：10.1071/c97149

  日期：——

  The asymmetric dihydroxylation of various alkenyl tetra-O-acetyl- β-D-glucopyranosides has given mixtures of diols which, in one instance, has yielded a pure diastereoisomer upon recrystallization. This optically pure diol has been converted into an episulfide, a putative inhibitor of β-D-glucan hydrolases

  各种烯基-O-四乙酰基-β-D-吡喃葡萄糖苷的不对称二羟基化 四-O-乙酰基-β-D-吡喃葡萄糖苷的不对称二羟基化反应产生了 二醇的混合物，其中有一次在重结晶时得到了纯的非对映异构体。 在重结晶时产生了一种纯的非对映异构体。这种光学纯度很高的二元醇被转化成一种 表硫醚--β-D-葡聚糖水解酶的一种假定抑制剂
• Evidence for cyclic bromonium ion transfer in electrophilic bromination of alkenes: Reaction of ω-alkenyl glycosides with aqueous N-bromosuccinimide
  作者：Robert Rodebaugh、Bert Fraser-Reid

  DOI：10.1016/s0040-4020(96)00349-3

  日期：1996.5

  that intermolecular Br+ transfer from a cyclic bromonium ion to an alkene occurs readily and can indeed overwhelm alternative reaction pathways. In the course of a study to determine which ω-alkenyl glycosides could serve as glycosyl donors, it was found that upon treatment with N-bromosuccinimide (NBS) in aqueous acetonitrile, under conditions in which an n-pentenyl glycoside underwent oxidative hydrolysis

  提供了证据来支持分子间Br +的理论从环溴离子转移到烯烃的转移很容易发生，并且确实会淹没其他反应途径。在确定哪些ω-烯基糖苷可以用作糖基供体的研究过程中，发现在N-溴丁二酰亚胺（NBS）在乙腈水溶液中处理的条件下，对正戊烯基糖苷进行氧化水解为相应的半缩醛，烯丙基，丁烯基和己烯基类似物产生了溴代醇加成产物。进一步发现，当制造戊烯基和己烯基类似物竞争不足量的NBS时，前者反应了，而后者显然没有改变。但是，两者均以相似的速率独立反应。另外，发现该现象是浓度依赖性的。这些结果与分子间，+从环溴离子到烯烃。
• The Synthesis of Active-Site Directed Inhibitors of Some β-Glucan Hydrolases
  作者：EB Rodriguez、RV Stick

  DOI：10.1071/ch9900665

  日期：——

  The 2,3-epoxypropyl, 3,4-epoxybutyl and 4,5-epoxypentyl β-glycosides of D-glucose, cellobiose and laminaribiose have been prepared. As well, the 4,5-epoxypentyl β-glycosides of cellotriose, laminaritriose and two other trisaccharides have been synthesized. 3,4-Epoxybutyl β-cellobioside has also been prepared with a 14C-label in the cellobiose residue.

  制备出了 D-葡萄糖、纤维生物糖和片状生物糖的 2,3-环氧丙基、3,4-环氧丁基和 4,5-环氧戊基 β-糖苷。此外，还合成了纤维三糖、片状三糖和另外两种三糖的 4,5-环氧戊基 β-糖苷。此外，还制备了 3,4-环氧丁基 β-纤维二糖苷，并在纤维二糖残基中添加了 14C 标记。