isopropyl 3,4,6-tri-O-benzyl-β-D-arabino-hexopyranosid-2-ulose | 158818-97-4

• 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-benzyl-β-D-arabino-hexopyranosid-2-ulose
• 英文别名: (2R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-propan-2-yloxyoxan-3-one
• CAS: 158818-97-4
• 化学式: C₃₀H₃₄O₆
• 分子量: 490.596
• InChiKey: RFLWRXLLZLSEGE-PYYPWFDZSA-N

物化性质

• 沸点：
  613.0±55.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  isopropyl 3,4,6-tri-O-benzyl-β-D-arabino-hexopyranosid-2-ulose 在 palladium on activated charcoal 吡啶 、 sodium tetrahydroborate 、 氢气 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 生成 iso-propyl 2,3,4,6-tetra-O-acetyl-β-D-mannopyranoside
  参考文献：
  名称：

  Experimental evidence on the hydroxymethyl group conformation in alkyl β-d-mannopyranosides

  摘要：

  A rotational population Study of the hydroxymethyl group of alkyl beta-D-mannopyranosides was performed by means of CD and NMR spectroscopy. Three different benzyl, acetyl, and p-bromobenzoyl series of alkyl beta-D-mannopyranosides with different chiral and nonchiral aglycons were synthesized and analyzed. Different rotational populations were observed for each series by changing the structure of the aglycon. The results showed a clear correlation between the rotational population of the hydroxymethyl group around the C5-C6 bond and the pK(a) of the bonded alcohol (aglycon). The population of the gt rotamer gradually increased as the pK(a) increased while that of the gg rotamer decreased and the population of the tg rotamer remained almost constant. This is explained by the exo-anomeric effect. For chiral alkyl derivatives, the results also showed a close dependence on the absolute configuration of the aglycon. Comparison of rotational population anomers revealed the dependence or the hydroxymethyl group on the anomeric configuration and a greater dependence on the aglycon structure in the beta anomers. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.06.019
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-1,2-O-(S)-(1-ethoxyethylidene)-α-D-glucopyranose 在 吡啶 、 氢氧化钾 、 N-溴代丁二酰亚胺(NBS) 、 3 A molecular sieve 、 silver carbonate 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 4.54h， 生成 isopropyl 3,4,6-tri-O-benzyl-β-D-arabino-hexopyranosid-2-ulose
  参考文献：
  名称：

  3,4,6-Tri-O-benzyl-.alpha.-D-arabino-hexopyranos-2-ulosyl Bromide: A Versatile Glycosyl Donor for the Efficient Generation of .beta.-D-Mannopyranosidic Linkages

  摘要：

  An expedient four-step sequence is described for the conversion of acetobromoglucose into the title 2-oxohexosyl (''ulosyl'') bromide 4. Due to its O-benzyl protection, 4 is considerably more reactive than its acylated analogs 1-3: Ag2CO3-promoted glycosidations with 2-propanol, diacetone-galactose, and methyl 2,3-O-isopropylidene-alpha-L-rhamnoside are complete within minutes and, in addition, are endowed with beta-specificity. This renders ulosyl bromide 4 a most propitious, indirect beta-D-mannosyl donor, inasmuch as the borohydride reduction of the beta-D-glycosiduloses formed (14-16 --> 19, 21, and 22) proceeds with manno selectivities of >20:1. Comparative evaluation of the manno/gluco ratios obtained in all 21 beta-D-arabino hexosidulose reductions (Table 1) reveals the 3-O-blocking group to have a pronounced effect on the outcome: >20:1 in cases with a 3-O-benzyl group versus only 2:1 to 3:1 in the presence of 3-O-acyl functions.

  DOI：

  10.1021/jo00101a035

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.
• Experimental evidence on the hydroxymethyl group conformation in alkyl β-d-mannopyranosides
  作者：Carlos Mayato、Rosa Dorta、Jesús Vázquez

  DOI：10.1016/j.tetasy.2004.06.019

  日期：2004.8

  A rotational population Study of the hydroxymethyl group of alkyl beta-D-mannopyranosides was performed by means of CD and NMR spectroscopy. Three different benzyl, acetyl, and p-bromobenzoyl series of alkyl beta-D-mannopyranosides with different chiral and nonchiral aglycons were synthesized and analyzed. Different rotational populations were observed for each series by changing the structure of the aglycon. The results showed a clear correlation between the rotational population of the hydroxymethyl group around the C5-C6 bond and the pK(a) of the bonded alcohol (aglycon). The population of the gt rotamer gradually increased as the pK(a) increased while that of the gg rotamer decreased and the population of the tg rotamer remained almost constant. This is explained by the exo-anomeric effect. For chiral alkyl derivatives, the results also showed a close dependence on the absolute configuration of the aglycon. Comparison of rotational population anomers revealed the dependence or the hydroxymethyl group on the anomeric configuration and a greater dependence on the aglycon structure in the beta anomers. (C) 2004 Elsevier Ltd. All rights reserved.
• 3,4,6-Tri-O-benzyl-.alpha.-D-arabino-hexopyranos-2-ulosyl Bromide: A Versatile Glycosyl Donor for the Efficient Generation of .beta.-D-Mannopyranosidic Linkages
  作者：Frieder W. Lichtenthaler、Thomas Schneider-Adams

  DOI：10.1021/jo00101a035

  日期：1994.11

  An expedient four-step sequence is described for the conversion of acetobromoglucose into the title 2-oxohexosyl (''ulosyl'') bromide 4. Due to its O-benzyl protection, 4 is considerably more reactive than its acylated analogs 1-3: Ag2CO3-promoted glycosidations with 2-propanol, diacetone-galactose, and methyl 2,3-O-isopropylidene-alpha-L-rhamnoside are complete within minutes and, in addition, are endowed with beta-specificity. This renders ulosyl bromide 4 a most propitious, indirect beta-D-mannosyl donor, inasmuch as the borohydride reduction of the beta-D-glycosiduloses formed (14-16 --> 19, 21, and 22) proceeds with manno selectivities of >20:1. Comparative evaluation of the manno/gluco ratios obtained in all 21 beta-D-arabino hexosidulose reductions (Table 1) reveals the 3-O-blocking group to have a pronounced effect on the outcome: >20:1 in cases with a 3-O-benzyl group versus only 2:1 to 3:1 in the presence of 3-O-acyl functions.