6-O-(3,4,6-tri-O-benzoyl-β-D-arabino-hexopyranos-2-ulosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose | 562075-69-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-O-(3,4,6-tri-O-benzoyl-β-D-arabino-hexopyranos-2-ulosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
• 英文别名: 1,2:3,4-di-O-isopropylidene-6-O-(3',4',6'-tri-O-benzoyl-2-deoxy-β-D-arabino-hexopyranos-2-ulosyl)-D-galactopyranose；[(2R,3R,4S,6R)-3,4-dibenzoyloxy-5-oxo-6-[[(1S,2R,6R,8R,9S)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecan-8-yl]methoxy]oxan-2-yl]methyl benzoate
• CAS: 562075-69-8
• 化学式: C₃₉H₄₀O₁₄
• 分子量: 732.738
• InChiKey: KJMRFZIIYBAWJJ-NVZNTMPZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  53
• 可旋转键数：
  13
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  161
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  6-O-(3,4,6-tri-O-benzoyl-β-D-arabino-hexopyranos-2-ulosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose 在 potassium tri-sec-butyl-borohydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.02h， 以580 mg的产率得到6-O-(3,4,6-tri-O-benzoyl-β-D-mannopyranosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  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
• 作为产物：
  描述：

  3,4,6-tri-O-benzoyl-α-D-arabino-hexopyranosyl-2-ulose bromide 、 双丙酮半乳糖 在 3 A molecular sieve 、 silver carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以83%的产率得到6-O-(3,4,6-tri-O-benzoyl-β-D-arabino-hexopyranos-2-ulosyl)-1,2:3,4-di-O-isopropylidene-α-D-galactopyranose
  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。
• manno- versus gluco-Selectivity in reductions of 2-keto-β-d-arabino-hexopyranosides
  作者：Frieder W. Lichtenthaler、Matthias Lergenmüller、Siegfried Peters、Zsolt Varga

  DOI：10.1016/s0957-4166(03)00028-4

  日期：2003.3

  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.