2,3,4,6-tetra-O-acetyl-1-deoxy-1-bromo-β-D-glycopyranosyl cyanide | 82469-74-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2,3,4,6-tetra-O-acetyl-1-deoxy-1-bromo-β-D-glycopyranosyl cyanide
• 英文别名: 2,3,4,6-Tetra-O-acetyl-1-bromo-D-glucopyranosyl cyanide；2,3,4,6-Tetra-O-acetyl-1-bromo-D-glucosyl cyanide；[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-bromo-6-cyanooxan-2-yl]methyl acetate
• CAS: 82469-74-7
• 化学式: C₁₅H₁₈BrNO₉
• 分子量: 436.213
• InChiKey: HTTKGSLSIQMYRG-QMIVOQANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  138
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-1-deoxy-1-bromo-β-D-glycopyranosyl cyanide 在 水 、 四氯化钛 、 溶剂黄146 、 silver(l) oxide 作用下， 以 二甲基亚砜 为溶剂， 反应 144.0h， 生成 C-(2,3,4,6-tetra-O-acetyl-1-hydroxy-β-D-glucopyranosyl)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：

  3,4,5,7-tetra-O-acetyl-2,6-anhydro-D-glycero-D-gulo-heptononitrile 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 四氯化碳 为溶剂， 以83%的产率得到2,3,4,6-tetra-O-acetyl-1-deoxy-1-bromo-β-D-glycopyranosyl cyanide
  参考文献：
  名称：

  Lichtenthaler, Frieder W.; Jarglis, Pan, Angewandte Chemie, 1982, vol. 94, # 8, p. 643 - 644

  摘要：

  DOI：

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 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
• Efficient inhibition of muscle and liver glycogen phosphorylases by a new glucopyranosylidene-spiro-thiohydantoin
  作者：Erzsébet Ősz、László Somsák、László Szilágyi、László Kovács、Tibor Docsa、Béla Tóth、Pál Gergely

  DOI：10.1016/s0960-894x(99)00192-4

  日期：1999.5

  Reaction of C-(1-bromo-1-deoxy-beta-D-glucopyranosyl)forma 2 with thiocyanate ions was the key step of a short synthesis of D-glucopyranosylidene-spiro-thiohydantoin 7 which proved to be a potent inhibitor of muscle and liver glycogen phosphorylases. (C) 1999 Elsevier Science Ltd. All rights reserved.
• 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：——