4,6-di-O-benzoyl-3-O-benzyl-1-thio-α-D-arabino-hexopyranosid-2-ulosyl bromide | 205869-82-5

• 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: 4,6-di-O-benzoyl-3-O-benzyl-1-thio-α-D-arabino-hexopyranosid-2-ulosyl bromide
• 英文别名: 4,6-di-O-benzoyl-3-O-benzyl-α-D-arabino-hexopyranos-2-ulosyl bromide
• CAS: 205869-82-5
• 化学式: C₂₇H₂₃BrO₇
• 分子量: 539.379
• InChiKey: WHQGKBLQHFBZKK-DFXJHMEVSA-N

物化性质

• 沸点：
  632.6±55.0 °C(Predicted)
• 密度：
  1.46±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.34
• 重原子数：
  35.0
• 可旋转键数：
  8.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  4,6-di-O-benzoyl-3-O-benzyl-1-thio-α-D-arabino-hexopyranosid-2-ulosyl bromide 在 palladium on activated charcoal 吡啶 、 sodium tetrahydroborate 、 4 A molecular sieve 、 氢气 、 sodium methylate 、 溶剂黄146 、 silver carbonate 、 mercury dibromide 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 40.33h， 生成 octyl 6-O-(α-D-mannopyranosyl)-β-D-mannopyranoside
  参考文献：
  名称：

  4,6-di-O-benzoyl-3-O-benzyl-α-d-arabino-hexopyranos-2-ulosyl bromide: A conveniently accessible glycosyl donor for the expedient construction of diantennary β-d-mannosides branched at O-3 and O-6

  摘要：

  A concise practical, large scale-adaptable six-step sequence has been developed for the transformation of diacetone-glucose into 4,6-di-O-benzoyl-3-O-benzyl-alpha-D-arabino-hexo-pyranos-2 -ulosyl bromide (7), a most useful indirect beta-D-mannosyl donor as its blocking group pattern allows the construction of biologically relevant beta-D-mannosides branched at O-3 and O-6. The broad utility of this new ulosyl bromide 7 resides in its high anomeric reactivity, and in the ease and uniformity with which beta-stereocontrol can be achieved over both, glycosidations and carbonyl reduction of the beta-ulosides formed: Koenigs-Knorr conditions exclusively provide beta-glycosiduloses, hydride reduction of their carbonyl functions proceeds with high stereoselectivities (> 20:1) in favor of the beta-D-mannosides, These preparatively auspicious properties are materialized in an efficient, straightforward synthesis of alpha-D-Manp-(1 --> 6)-[alpha-D-Manp-(1 --> 3)]-beta-D-Manp-(1 --> O)-Octyl, the 3,6-O-branched core-mannotrioside carrying an octyl spacer instead of the chitobiosyl unit. (C) 1998 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(97)00249-8
• 作为产物：
  描述：

  3-O-benzyl-1,2;5,6-di-O-isopropylidene-α-D-glucofuranoside 在 吡啶 、 N-溴代丁二酰亚胺(NBS) 、 乙醇 、 4 A molecular sieve 、 Dowex 50 (H⁽¹⁺⁾) 、 氢溴酸 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 28.17h， 生成 4,6-di-O-benzoyl-3-O-benzyl-1-thio-α-D-arabino-hexopyranosid-2-ulosyl bromide
  参考文献：
  名称：

  4,6-di-O-benzoyl-3-O-benzyl-α-d-arabino-hexopyranos-2-ulosyl bromide: A conveniently accessible glycosyl donor for the expedient construction of diantennary β-d-mannosides branched at O-3 and O-6

  摘要：

  A concise practical, large scale-adaptable six-step sequence has been developed for the transformation of diacetone-glucose into 4,6-di-O-benzoyl-3-O-benzyl-alpha-D-arabino-hexo-pyranos-2 -ulosyl bromide (7), a most useful indirect beta-D-mannosyl donor as its blocking group pattern allows the construction of biologically relevant beta-D-mannosides branched at O-3 and O-6. The broad utility of this new ulosyl bromide 7 resides in its high anomeric reactivity, and in the ease and uniformity with which beta-stereocontrol can be achieved over both, glycosidations and carbonyl reduction of the beta-ulosides formed: Koenigs-Knorr conditions exclusively provide beta-glycosiduloses, hydride reduction of their carbonyl functions proceeds with high stereoselectivities (> 20:1) in favor of the beta-D-mannosides, These preparatively auspicious properties are materialized in an efficient, straightforward synthesis of alpha-D-Manp-(1 --> 6)-[alpha-D-Manp-(1 --> 3)]-beta-D-Manp-(1 --> O)-Octyl, the 3,6-O-branched core-mannotrioside carrying an octyl spacer instead of the chitobiosyl unit. (C) 1998 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(97)00249-8

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.