O-acetyl-C-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)formamidoxime | 915313-34-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: O-acetyl-C-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)formamidoxime
• 英文别名: [(2R,3R,4R,5S,6S)-6-[(Z)-N'-acetyloxycarbamimidoyl]-3,4,5-tribenzoyloxyoxan-2-yl]methyl benzoate
• CAS: 915313-34-7
• 化学式: C₃₇H₃₂N₂O₁₁
• 分子量: 680.668
• InChiKey: DPMVHPRDJICCGX-HXBJCGEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  50
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  179
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  O-acetyl-C-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)formamidoxime 以 1,4-二氧六环 为溶剂， 反应 48.0h， 以50%的产率得到5-methyl-3-C-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)-1,2,4-oxadiazole
  参考文献：
  名称：

  寻找糖原磷酸化酶抑制剂：从 β-D-吡喃葡萄糖基氰化物中得到 5-取代的 3-C-吡喃葡萄糖基-1,2,4-恶二唑，在 O-酰基胺肟中间体环化时

  摘要：

  在用羟胺、苄基和苯甲酰基保护的 β-D-吡喃葡萄糖基氰化物处理后，有效地提供了相应的酰胺肟。它们在羧酸或酰氯的存在下通过 O-酰化反应提供苄基和苯甲酰保护的 O-酰氨基肟。后者被隔离并充分表征。O-酰氨基肟的热环化产生了相应的 5-取代 3-C-β-D-吡喃葡萄糖基-1,2,4-恶二唑，无论是在“一锅”程序（苄基化系列）中，还是分两步（苯甲酰化）系列）。针对糖原磷酸化酶 (GP) 测定了在脱苯甲酰化后获得的十二个 5-取代的 1,2,4-恶二唑。3-C-(β-D-吡喃葡萄糖基)-5-(2-萘基)-1,2,4-恶二唑是兔肌糖原磷酸化酶 b 的最佳抑制剂 (Ki = 38.4 ±3.0 μM)。(© Wiley-VCH Verlag GmbH & Co. KGaA,

  DOI：

  10.1002/ejoc.200600073
• 作为产物：
  描述：

  (2R,3R,4R,5S,6S)-2-[(苯甲酰氧基)甲基]-6-氰基四氢-2H-吡喃-3,4,5-三基三苯甲酸酯 在 吡啶 、 盐酸羟胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 24.0h， 生成 O-acetyl-C-(2,3,4,6-tetra-O-benzoyl-β-D-glucopyranosyl)formamidoxime
  参考文献：
  名称：

  寻找糖原磷酸化酶抑制剂：从 β-D-吡喃葡萄糖基氰化物中得到 5-取代的 3-C-吡喃葡萄糖基-1,2,4-恶二唑，在 O-酰基胺肟中间体环化时

  摘要：

  在用羟胺、苄基和苯甲酰基保护的 β-D-吡喃葡萄糖基氰化物处理后，有效地提供了相应的酰胺肟。它们在羧酸或酰氯的存在下通过 O-酰化反应提供苄基和苯甲酰保护的 O-酰氨基肟。后者被隔离并充分表征。O-酰氨基肟的热环化产生了相应的 5-取代 3-C-β-D-吡喃葡萄糖基-1,2,4-恶二唑，无论是在“一锅”程序（苄基化系列）中，还是分两步（苯甲酰化）系列）。针对糖原磷酸化酶 (GP) 测定了在脱苯甲酰化后获得的十二个 5-取代的 1,2,4-恶二唑。3-C-(β-D-吡喃葡萄糖基)-5-(2-萘基)-1,2,4-恶二唑是兔肌糖原磷酸化酶 b 的最佳抑制剂 (Ki = 38.4 ±3.0 μM)。(© Wiley-VCH Verlag GmbH & Co. KGaA,

  DOI：

  10.1002/ejoc.200600073

文献信息

• C-(β-d-Glucopyranosyl)formamidrazones, formic acid hydrazides and their transformations into 3-(β-d-glucopyranosyl)-5-substituted-1,2,4-triazoles: a synthetic and computational study
  作者：Éva Bokor、Attila Fekete、Gergely Varga、Béla Szőcs、Katalin Czifrák、István Komáromi、László Somsák

  DOI：10.1016/j.tet.2013.09.099

  日期：2013.12

  Synthesis of O-perbenzoylated 3-(beta-D-glucopyranosyl)-5-substituted-1,2,4-triazoles, precursors of potent inhibitors of glycogen phosphorylase, was studied by ring closures of N-1-acyl-carboxamidrazone type intermediates. Reactions of C-(beta-D-glucopyranosyl)formimidate or C-(beta-D-glucopyranosyl)formamidine with acid hydrazides as well as acylation of C-(beta-D-glucopyranosyl)formamidrazone by acid chlorides unexpectedly gave the corresponding 1,3,4-oxadiazoles instead of 1,2,4-triazoles. The desired triazoles were obtained in reactions of C-(beta-D-glucopyranosyl)formamidine or C-(beta-D-glucopyranosyl) formyl chloride with arenecarboxamidrazones, and also in acylations of N-1-tosyl-C-(beta-D-glucopyranosyl)formamidrazone with acid chlorides. Theoretical calculations (B3LYP and M06-2X OFT with the standard 6-31G(d,p) basis set) on simple model compounds with methyl and phenyl substituents to understand the bifurcation of the ring closure of N-1-acyl-carboxamidrazones indicated that in general the reaction led to 1,2,4-triazoles. However, the probability of the 1,3,4-oxadiazole forming pathway was shown to be significantly higher with N-1-benzoyl-acetamidrazones, which were closest analogues of the intermediates resulting in C-glucosyl-1,3,4-oxadiazoles. It was thereby demonstrated that the substitution pattern of the N-1-acyl-carboxamidrazones played a fundamental role in determining the direction of the ring closing reaction. (C) 2013 Elsevier Ltd. All rights reserved.