iso-propyl 3,4,6-tri-O-benzyl-β-D-mannopyranoside | 138181-77-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: iso-propyl 3,4,6-tri-O-benzyl-β-D-mannopyranoside
• 英文别名: (2R,3S,4R,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-propan-2-yloxyoxan-3-ol
• CAS: 138181-77-8
• 化学式: C₃₀H₃₆O₆
• 分子量: 492.612
• InChiKey: CTEMNFRCFHGESM-ONBQWJCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  iso-propyl 3,4,6-tri-O-benzyl-β-D-mannopyranoside 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 5.0h， 以98%的产率得到isopropyl β-D-mannopyranoside
  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
• 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 、 sodium tetrahydroborate 、 N-溴代丁二酰亚胺(NBS) 、 3 A molecular sieve 、 silver carbonate 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 6.54h， 生成 iso-propyl 3,4,6-tri-O-benzyl-β-D-mannopyranoside
  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

• 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.
• Stereocontrolled synthesis of disaccharides via the temporary silicon connection
  作者：Gilbert Stork、Guncheol Kim

  DOI：10.1021/ja00029a047

  日期：1992.1
• 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.