2,3,4-Tri-O-acetyl-1-bromo-D-xylopyranosyl cyanide | 83497-43-2

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 2,3,4-Tri-O-acetyl-1-bromo-D-xylopyranosyl cyanide
• 英文别名: 2,3,4-tri-O-acetyl-1-deoxy-1-bromo-β-D-xylopyranosyl cyanide；2,3,4-Tri-O-acetyl-1-bromo-D-xylosyl cyanide；[(3R,4S,5R,6R)-4,5-diacetyloxy-6-bromo-6-cyanooxan-3-yl] acetate
• CAS: 83497-43-2
• 化学式: C₁₂H₁₄BrNO₇
• 分子量: 364.15
• InChiKey: PWDCJWOBYXDRAR-KXNHARMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  112
• 氢给体数：
  0
• 氢受体数：
  8

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  2,3,4-Tri-O-acetyl-1-bromo-D-xylopyranosyl cyanide 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 四氯化钛 、 溶剂黄146 作用下， 以 硝基甲烷 为溶剂， 反应 148.0h， 生成 C-(2,3,4-tri-O-acetyl-1-hydroxy-β-D-xylopyranosyl)formamide
  参考文献：
  名称：

  Synthesis of and a Comparative Study on the Inhibition of Muscle and Liver Glycogen Phosphorylases by Epimeric Pairs of d-Gluco- and d-Xylopyranosylidene-spiro-(thio)hydantoins and N-(d-Glucopyranosyl) Amides

  摘要：

  D-Gluco- and D-xylopyranosylidene-spiro-hydantoins and -thiohydantoins were prepared from the parent sugars in a six-step, highly chemo-, regio-, and stereoselective procedure. In the key step of the syntheses C-(1-bromo-1-deoxy-beta -D-glycopyranosyl)formamides were reacted with cyanate ion to give spiro-hydantoins with a retained configuration at the anomeric center as the major products. On the other hand, thiocyanate ions gave spiro-thiohydantoins with an inverted anomeric carbon as the only products. On the basis of radical inhibition studies, a mechanistic rationale was proposed to explain this unique stereoselectivity and the formation of C-(1-hydroxy-beta -D-glycopyranosyl)formamides as byproducts. Enzyme assays with a and b forms of muscle and liver glycogen phosphorylases showed spiro-hydantoin 12 and spiro-thiohydantoin 14 to be the best and equipotent inhibitors with K-i values in the low micromolar range. The study of epimeric pairs of D-gluco and D-Xylo configurated spiro-hydantoins and N-(D-glucopyranosyl)amides corroborated the role of specific hydrogen bridges in binding the inhibitors to the enzyme.

  DOI：

  10.1021/jm010892t
• 作为产物：
  描述：

  1-deoxy-2,3,4,6-tetra-O-acetyl-β-D-xylopyranosyl cyanide 在 N-溴代丁二酰亚胺(NBS) 、 过氧化氢苯甲酰 作用下， 以 四氯化碳 为溶剂， 以42%的产率得到2,3,4-Tri-O-acetyl-1-bromo-D-xylopyranosyl cyanide
  参考文献：
  名称：

  Bromination of acetylated 2,5-anhydro-aldononitriles at the anomeric centre using N-bromosuccinimide: synthesis of 2,3,4,6-tetra-O-acetyl-1-bromo-d-galactopyranosyl cyanide and its d-xylopyranosyl analogue

  摘要：

  DOI：

  10.1016/s0008-6215(00)80746-6

文献信息

• Synthesis and some transformations of 1-azido-glycopyranosyl cyanides-precursors of anomeric α-amino acids
  作者：László Somsák、Erzsébet Sós、Zoltán Györgydeák、Jean-Pierre Praly、Gérard Descotes

  DOI：10.1016/0040-4020(96)00440-1

  日期：1996.7

  Acetylated 1-azido-glycopyranosyl cyanides (of the (1R)- 2, and 16, 5, 7, (1R)- 11, and 12 configurations) and 19 were prepared from acetylated 1-halogeno-d-glycopyranosyl cyanides and formamide, resp., by sodium azide in dimethyl sulfoxide. Acetylated (1S)- 14 and (1R)- 15 1-chloro-d-galactopyranosyl cyanides were obtained from cyanide by lithium chloride in dimethyl sulfoxide. 1,3-Dipolar cycloaddition

  乙酰化的1-叠氮基吡喃葡萄糖基氰化物（在（1 - [R ）- 2，和16，5，7，（1 - [R ）- 11和12的配置）和19是从乙酰化制备1 β-卤代-d吡喃葡萄糖氰化物和甲酰胺，分别是叠氮化钠在二甲基亚砜中。通过二甲基亚砜中的氯化锂从氰化物获得乙酰化的（1 S）-14和（1 R）-15 1-氯-d-吡喃半乳糖基氰化物。叠氮化物离子与2的氰基的1,3-偶极环加成和16得到乙酰化的5-（1-叠氮基-1-脱氧-α-和-β-d-吡喃半乳糖基）四唑3和17，而乙炔基二羧酸二甲酯到2的叠氮基部分得到乙酰化的1-甲基二甲基。 （1-叠氮基-1-脱氧-β-d-吡喃半乳糖基）-1,2,3-三唑-4,5-二羧酸20。由乙氧基氯转化3，得到乙酰化的2-（1-叠氮基-1-脱氧-α-d-吡喃半乳糖基）-1,3,4-乙二唑-5-羧酸乙酯21。
• Preparation of acetylated C-(1-bromo-d-glycosyl) heterocycles and 1-bromo-d-glycosyl cyanides
  作者：László Somsák、Gyula Batta、István Farkas

  DOI：10.1016/0008-6215(83)88354-2

  日期：1983.12

  Abstract The reaction of acetylated C -( d -glycosyl) heterocycles and d -glycosyl cyanides with either N -bromosuccinimide in hot carbon tetrachloride or bromine under irradiation resulted in bromination at the anomeric carbon atom. The location of the bromine substituent and the conformations of these products were determined by n.m.r. spectroscopy. Absolute configurations of the bromo compounds

  摘要乙酰化的C-（d-糖基）杂环与d-糖基氰化物与N-溴丁二酰亚胺在热四氯化碳或溴中的辐射下反应导致异头碳原子溴化。溴取代基的位置和这些产物的构象通过核磁共振光谱法确定。建立了溴化合物的绝对构型。
• Preparation of acetylated 1-fluoroglycopyranosyl cyanides
  作者：Viktor Gyóllai、László Somsák、Zoltán Györgydeák

  DOI：10.1016/s0040-4020(98)00813-8

  日期：1998.10

  corresponding inverted 1-fluoroglycosyl cyanides (4 and 6, respectively) together with significant amounts of 1-cyano-2-hydroxy-glycals (9 and 10, respectively). Silver tetrafluoroborate in toluene at room temperature converted 2 and 3 into the 1-fluoroglycosyl cyanides (7 and 8, respectively) of retained anomeric configuration. 1-Chloro-1-deoxy-α-d-galactopyranosyl cyanide (11) also gave 7 with silver fluoride

  β-d-半乳糖（2）和α-d-阿拉伯糖（12）构型的乙酰化1-bromo-1-deoxy-glycopyranosyl氰化物在室温下与氟化银在乙腈中的反应得到相应的1-deoxy-1-fluoroglycopyranosyl氰化物（分别为5和13），并带有异头中心。在相似的条件下，β-d-葡萄糖（1）和β-d- xylo（3）化合物产生相应的反向1-氟糖基氰化物（分别为4和6）以及大量的1-氰基-2-羟基-糖基（分别为9和10）。室温下在甲苯中的四氟硼酸银将2和3转换为保留的端基异构体构型的1-氟糖基氰化物（分别为7和8）。1-氟-1-脱氧-α-d-吡喃半乳糖基氰化物（11）在回流温度下在乙腈中与氟化银一起得到7。1-脱氧-1-氟-戊吡喃糖基氰化物6、8和13的构象平衡反映了氟和氰基所产生的端基异构作用的反作用。1-脱氧-1-氟-α-d-吡喃半乳糖基氰被证明是弱竞争抑制剂，如果大肠杆菌β-d-半乳糖苷酶（K
• Preparation of acetylated 2,6-anhydrohept(hex)-2-enono-nitriles (1-cyano-2-hydroxyglycals)
  作者：László Somsák、Etelka Papp、Gyula Batta、István Farkas

  DOI：10.1016/0008-6215(91)84157-a

  日期：1991.4
• Korth, Hans-Gert; Praly, Jean-Pierre; Somsak, Laszlo, Chemische Berichte, 1990, vol. 123, # 5, p. 1155 - 1160
  作者：Korth, Hans-Gert、Praly, Jean-Pierre、Somsak, Laszlo、Sustmann, Reiner

  DOI：——

  日期：——