isopropyl 3,4,6-tri-O-benzoyl-β-arabino-hexopyranosid-2-ulose | 87713-52-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: isopropyl 3,4,6-tri-O-benzoyl-β-arabino-hexopyranosid-2-ulose
• 英文别名: [(2R,3R,4S,6R)-3,4-dibenzoyloxy-5-oxo-6-propan-2-yloxyoxan-2-yl]methyl benzoate
• CAS: 87713-52-8
• 化学式: C₃₀H₂₈O₉
• 分子量: 532.547
• InChiKey: NXVGZYQRMSCWCV-NYBSAPDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  39
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  isopropyl 3,4,6-tri-O-benzoyl-β-arabino-hexopyranosid-2-ulose 在 碳酸氢钠 作用下， 以 丙酮 为溶剂， 反应 10.0h， 生成 ((2S,6R)-4-(benzoyloxy)-6-isopropoxy-5-oxo-5,6-dihydro-2H-pyran-2-yl)methyl benzoate
  参考文献：
  名称：

  Lichtenthaler, Frieder W.; Cuny, Eckehard; Weprek, Sabine, Angewandte Chemie, 1983, vol. 95, # 11, p. 906 - 908

  摘要：

  DOI：
• 作为产物：
  描述：

  (2R,3R,4S,6S)-2-((benzoyloxy)methyl)-6-bromo-5-oxotetrahydro-2H-pyran-3,4-diyl dibenzoate 、 异丙醇 在 3 A molecular sieve 、 silver carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 isopropyl 3,4,6-tri-O-benzoyl-β-arabino-hexopyranosid-2-ulose
  参考文献：
  名称：

  manno- versus gluco-Selectivity in reductions of 2-keto-β-d-arabino-hexopyranosides

  摘要：

  Tri-sec-butylborohydrides (L- or K-Selectride) reduce the carbonyl group in acylated 2-keto-beta-D-arabino-hexopyranosides to beta-D-mannosides in an essentially stereospecific fashion, whereas borane reduction gives the 2-epimeric beta-D-glucosides with high preference. As preparative yields are in the 70-85% range, the ulosyl donor approach can thus be utilized for the straightforward construction of oligosaccharides containing either beta-D-Man or beta-D-Glc units. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00028-4

文献信息

• E versus Z geometry in β-d-arabino-hexopyranosidulose oximes
  作者：Matthias Lergenmüller、Ulrich Kläres、Frieder W. Lichtenthaler

  DOI：10.1016/j.carres.2009.08.007

  日期：2009.11

  this way and for which the oxime geometry has not been addressed explicitly, are the Z-oximes throughout. By contrast, oximation of beta-D-hexopyranosid-2-uloses leads to mixtures of E and Z oximes readily separable and structurally verifiable by (1)H and (13)C NMR. Configurational assignments rested on comparative evaluation of NMR data of E and Z isomers, and, most notably on an X-ray structural analysis

  过酰基化的2Z-苯甲酰氧基亚氨基-甘露型核糖基溴化物的Koenigs-Knorr型糖基化始终伴随着Z几何形状的保留。因此，以这种方式制备的肟的几何形状尚未明确解决的文献中的许多β-D-己二糖肟是整个Z-肟。相比之下，β-D-己基吡喃二糖基-2-uloses的肟化导致E和Z肟的混合物易于通过（1）H和（13）C NMR分离和结构验证。构型分配取决于对E和Z异构体的NMR数据的比较评估，并且最显着的是对Pivaloylated异丙基2E-苯甲酰氧基亚氨基-2-脱氧-β-D-阿拉伯糖基己吡喃糖苷的X射线结构分析，揭示了异常现象（1吡喃环的）S（5）＝（1，4）B构象。
• Various Glycosyl Donors with a Ketone or Oxime Function next to the Anomeric Centre: Facile Preparation and Evaluation of their Selectivities in Glycosidations
  作者：Frieder W. Lichtenthaler、Ulrich Kläres、Matthias Lergenmüller、Sabine Schwidetzky

  DOI：10.1055/s-1992-34167

  日期：——

  An efficient one-pot procedure is described for the conversion of a variety of hydroxyglycal esters to their 2-oxoglycosyl bromides which simply comprises of brief treatment with N-bromosuccinimide/methanol at ambient temperature. Exhibiting comparably low anomeric reactivity in glycosidation reactions, these ulosyl bromides, as well as their 2-benzoyloxyimino analogs, can readily be transformed into a range of more reactive glycosyl donors with iodine, pentenyloxy, ethylthio and dithiocarbamoyl residues at the anomeric centre, such that any ß-selective glycosidation may be successfullv achieved.

  描述了一种高效的一锅法步骤，用于将多种羟基甘油酯转化为其2-氧基糖苷溴化物，该过程仅涉及在室温下用N-溴琥珀酰亚胺/甲醇进行简短处理。这些氧基糖苷溴化物在糖苷化反应中表现出相对较低的异构体反应性，同时，它们的2-苯甲氧羰基亚氨基类似物也可以很容易地转化为一系列更具反应性的糖苷供体，这些供体在异构体中心具有碘、戊烯氧、乙硫基和二硫氨基甲酰基残基，从而可以成功实现任何β选择性的糖苷化反应。