[(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-[(trimethyl-lambda5-phosphanylidene)amino]oxan-2-yl]methyl acetate | 353264-31-0

• 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: [(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-[(trimethyl-lambda5-phosphanylidene)amino]oxan-2-yl]methyl acetate
• 英文别名: [(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-[(trimethyl-λ5-phosphanylidene)amino]oxan-2-yl]methyl acetate
• CAS: 353264-31-0
• 化学式: C₁₇H₂₈NO₉P
• 分子量: 421.384
• InChiKey: PGMFPVPRZSOXNO-NQNKBUKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  28
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  127
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-[(trimethyl-lambda5-phosphanylidene)amino]oxan-2-yl]methyl acetate 在 sodium methylate 作用下， 以 二氯甲烷 为溶剂， 生成 methyl 3-(N-β-D-glucopyranosyl-carbamoyl)-(E)-propenoate
  参考文献：
  名称：

  Synthesis of N-(β-d-glucopyranosyl) monoamides of dicarboxylic acids as potential inhibitors of glycogen phosphorylase

  摘要：

  O-Peracetylated N-(beta-D-glucopyranosyl)imino trimethylphosphorane obtained in situ from 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl azide and PMe3 was reacted with saturated and unsaturated aliphatic and aromatic dicarboxylic acids, or their anhydrides. or monoesters to give the corresponding N-(beta-D-glucopyranosyl) monoamides of dicarboxylic acids or derivatives. The acetyl protecting groups were removed according to the Zemplen protocol to give a series of compounds which showed moderate inhibitory effects against rabbit muscle glycogen phosphorylase b. The best inhibitor was 3-(N-beta-D-glucopyranosyl-carbamoy)propanoic acid (7) with K-i = 20 mu M. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2006.03.002
• 作为产物：
  描述：

  三甲基膦 、 1-azido-1-deoxy-β-D-glucopyranoside tetraacetate 以 二氯甲烷 、 甲苯 为溶剂， 生成 [(2R,3R,4S,5R,6R)-3,4,5-triacetyloxy-6-[(trimethyl-lambda5-phosphanylidene)amino]oxan-2-yl]methyl acetate
  参考文献：
  名称：

  葡萄糖基螺旋杂环作为糖原磷酸化酶的有效抑制剂

  摘要：

  通过NBS介导的相应的葡糖基-羟肟基硫代酸酯的螺环化，可以高收率制备葡糖基亚烷基-螺-1,4,2-氧杂噻唑。为了合成具有氮原子而不是硫原子的类似的吡喃吡喃基-螺-1,2,4-恶二唑啉，尝试的环化导致杂环的芳构化并带有吡喃糖基环。酶促测量表明，一些基于葡萄糖的抑制剂在微摩尔范围内具有活性。在 迄今为止已知的基于葡萄糖的抑制剂中，2-萘基取代的1,4,2-氧杂噻唑显示出对RMGPb的最佳抑制作用（K i = 160 nM）。

  DOI：

  10.1016/j.bmc.2009.05.080

文献信息

• Convenient syntheses of symmetrical and unsymmetrical glycosyl carbodiimides and N,N-bis(glycosyl)cyanamides
  作者：László Kovács、Erzsébet Ősz、Zoltán Györgydeák

  DOI：10.1016/s0008-6215(02)00108-8

  日期：2002.7

  carbon disulfide under mild conditions (room temperature, short reaction time) leads to symmetrical glycosyl carbodiimides. Addition of bis(trimethylsilyl)carbodiimide to peracetylated aldoses under the influence of SnCl(4) afforded N,N-bis(glycosyl)cyanamides for the first time. Readily accessible unsymmetrical N,N'-bis(glycosyl)thioureas can be desulfurated and transformed into the corresponding carbodiimides

  糖基三甲基次膦酰亚胺与二硫化碳在温和的条件下（室温，较短的反应时间）反应生成对称的糖基碳二亚胺。在SnCl（4）的影响下，向过乙酰化的醛糖中添加双（三甲基甲硅烷基）碳二亚胺，首次获得N，N-双（糖基）氰胺。容易获得的不对称N，N'-双（糖基）硫脲可以脱硫并在室温下使用HgO在CHCl（3）/水中的条件下转化为相应的碳二亚胺。
• Tethered derivatives of d-glucose and pentacyclic triterpenes for homo/heterobivalent inhibition of glycogen phosphorylase
  作者：Keguang Cheng、Jun Liu、Hongbin Sun、Éva Bokor、Katalin Czifrák、Bálint Kónya、Marietta Tóth、Tibor Docsa、Pál Gergely、László Somsák

  DOI：10.1039/b9nj00602h

  日期：——

  Propargyl esters of the C-28 carboxylic acids of pentacyclic triterpenes (oleanolic, ursolic, and maslinic acids) were coupled with 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl azide as well as N-(ω-azido-[C-2, C-6, and C-11]alkanoyl)-β-D-glucopyranosylamines under conditions of copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) to give tethered D-glucose–triterpene heteroconjugates. The O-acetyl protecting groups were removed by base-catalyzed hydrolysis. N-(ω-Azido-[C-2, C-6, C-11, and C-16]alkanoyl)-β-D-glucopyranosylamines were also tethered by 1,7-octadiyne under CuAAC conditions to furnish D-glucose homoconjugates. O-Deacetylation was carried out by the Zemplén protocol. The new compounds were assayed against rabbit muscle glycogen phosphorylase (RMGP) a or b enzymes. Some of the heteroconjugates inhibited the enzyme in the low micromolar range (IC50 values 40–70 μM), while the homoconjugates proved inefficient as inhibitors.

  五环三萜的 C-28 羧酸（齐墩果酸、熊果酸和山楂酸）的炔丙酯与 2,3,4,6-四-O-乙酰基-β-D-吡喃葡萄糖基叠氮化物以及 N-( ω-叠氮基-[C-2、C-6和C-11]烷酰基)-β-D-吡喃葡萄糖胺在铜(I)催化的叠氮化物-炔环加成(CuAAC)条件下生成束缚的D-葡萄糖-三萜异共轭物。通过碱催化水解除去O-乙酰基保护基团。 N-(ω-叠氮基-[C-2、C-6、C-11 和 C-16]烷酰基)-β-D-吡喃葡萄糖胺也在 CuAAC 条件下被 1,7-辛二炔束缚以提供 D-葡萄糖同缀合物。 O-脱乙酰化通过 Zemplén 方案进行。新化合物针对兔肌糖原磷酸化酶 (RMGP) a 或 b 酶进行了检测。一些杂合物在低微摩尔范围内抑制酶（IC50 值 40-70 μM），而同聚物作为抑制剂被证明是无效的。
• Amide-1,2,3-triazole bioisosterism: the glycogen phosphorylase case
  作者：Evangelia D. Chrysina、Éva Bokor、Kyra-Melinda Alexacou、Maria-Despoina Charavgi、George N. Oikonomakos、Spyros E. Zographos、Demetres D. Leonidas、Nikos G. Oikonomakos、László Somsák

  DOI：10.1016/j.tetasy.2009.03.021

  日期：2009.5

  Per-O-acetylated beta-D-glucopyranosyl azide was transformed into an intermediate iminophosphorane by PMe3 which was then acylated to N-acyl-beta-D-glucopyranosylamines. The same azide and substituted acetylenes gave 1-(beta-D-glucopyranosyl)-4-substituted-1,2,3-triazoles in Cu(I)-catalyzed azide-alkyne cycloadditions. Deprotection of these products by the Zemplen method furnished beta-D-Glc(p)-NHCO-R derivatives as well as 1-(beta-D-Glc(p))-4-R-1,2,3-triazoles which were evaluated as inhibitors of rabbit muscle glycogen phosphorylase b. Pairs of amides versus triazoles with the same R group displayed similar inhibition constants. X-ray crystallographic studies on the enzyme-inhibitor complexes revealed high similarities in the binding of pairs with R = 2-naphthyl and hydroxymethyl, while for the R = Ph and 1-naphthyl compounds a different orientation of the aromatic part and changes in the conformation of the 280s loop were observed. By this study new examples of amide-1,2,3-triazole bioisosteric relationship have been provided. (C) 2009 Elsevier Ltd. All rights reserved.