diethyl 2-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-ethylphosphonate | 201854-46-8

• 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: diethyl 2-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-ethylphosphonate
• 英文别名: diethyl 3-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)ethylphosphonate；[(2R,3R,4R,5S,6R)-3,4,5-triacetyloxy-6-(2-diethoxyphosphorylethyl)oxan-2-yl]methyl acetate
• CAS: 201854-46-8
• 化学式: C₂₀H₃₃O₁₂P
• 分子量: 496.449
• InChiKey: CHOMDLXCBWOWJC-OUUBHVDSSA-N

物化性质

• 沸点：
  538.0±40.0 °C(Predicted)
• 密度：
  1.25±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  33
• 可旋转键数：
  16
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  150
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  diethyl 2-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-ethylphosphonate 在 盐酸 、 ammonium hydroxide 作用下， 以 水 为溶剂， 反应 24.0h， 以100%的产率得到bis(ammonium) 2-(α-D-glucopyranosyl)ethylphosphonate
  参考文献：
  名称：

  Kinetic evaluation of glucose 1-phosphate analogues with a thymidylyltransferase using a continuous coupled enzyme assay

  摘要：

  我们开发了一种连续光谱光度测定动力学方法，用于检测PPi，并已将此方法应用于评估Cps2L（一种核苷酸转移酶）与五种合成底物类似物（2-6）的动力学。

  DOI：

  10.1039/c4ob02057j
• 作为产物：
  描述：

  1,2,3,4,6-alpha-D-葡萄糖五乙酸酯 在 三乙基硼 、 (1,3-dimethylimidazol-2-ylidene)borane 、 三氟化硼乙醚 、 氧气 、 间氯过氧苯甲酸 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 生成 diethyl 2-(2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl)-ethylphosphonate
  参考文献：
  名称：

  由糖基亚砜生成糖基自由基及其在C-连接的糖缀合物的合成中的用途。

  摘要：

  我们在这里报告了糖基亚砜与芳基碘化物部分相连的情况，是糖基自由基容易获得，对空气和水分稳定的前体。这些糖基亚砜可以通过快速和有效的分子内基团取代事件转化为糖基基团。使用这种类型的前体可以在温和的条件下合成各种复杂的C连接的糖缀合物。该反应可以在水性介质中进行，适合合成糖肽模拟物和碳水化合物-DNA共轭物。

  DOI：

  10.1002/anie.202009828

文献信息

• Towards α- or β-d-C-glycosyl compounds by tin-catalyzed addition of glycosyl radicals to acrylonitrile and vinylphosphonate, and flexible reduction of tetra-O-acetyl-α-d-glucopyranosyl bromide with cyanoborohydride
  作者：Jean-Pierre Praly、Azin Salek Ardakani、Isabelle Bruyère、Chrystelle Marie-Luce、Bing Bing Qin

  DOI：10.1016/s0008-6215(02)00052-6

  日期：2002.10

  These conditions led to 2-(α- d -manno-, and galactopyranosyl)-ethylphosphonates in 68 and 76% yields. Similarly, radical addition of acetylated 1-bromo-β- d -glucopyranosyl chloride ( 2 ) to acrylonitrile or diethyl vinylphosphonate afforded mainly intermediate chlorides which, upon radical reduction with excess tri- n -butyltin hydride, afforded the corresponding β anomers (40 and 38%, respectively)

  摘要在催化量的氯化三正丁基锡和过量的氰基硼氢化钠（或四正丁基铵）存在下，将乙酰化的α-d-吡喃葡萄糖基溴化物（1）光诱导自由基加成到丙烯腈或乙烯基膦酸二乙酯中，可以高效制备α-构型的壬腈和2-（α-d-吡喃葡萄糖基）-乙基膦酸酯（产率分别为79％和70％）。这些条件导致产率为68％和76％的2-（α-d-甘露糖基和吡喃并吡喃糖基）-乙基膦酸酯。类似地，将乙酰化的1-溴-β-d-吡喃葡萄糖基氯（2）自由基加成到丙烯腈或乙烯基膦酸二乙酯中，主要得到中间体氯化物，在用过量的三正丁基锡氢化物进行自由基还原后，得到相应的β异构体（40和分别由38％的CC和CH键形成。立体控制依赖于d -glycopyranos-1-yl自由基的α-立体选择性猝灭。我们还发现，在叔丁醇中用过量的NaBH 3 CN进行1的紫外光辐照，可得到1,3,4,6-四-O-乙酰基-2-脱氧-α-d-阿拉伯糖-己吡喃糖（结晶后占65％
• Non-isosteric C-glycosyl analogues of natural nucleotide diphosphate sugars as glycosyltransferase inhibitors
  作者：Sébastien Vidal、Isabelle Bruyère、Annie Malleron、Claudine Augé、Jean-Pierre Praly

  DOI：10.1016/j.bmc.2006.06.057

  日期：2006.11

  A series of C-glycosyl ethylphosphonophosphate analogues of UDP-Glc, UDP-Gal, UDP-GlcNAc and GDP-Fuc were synthesized from the corresponding C-glycosyl ethylphosphonic acids. Analogues were obtained as alpha-anomers through either diastereoselective photo-induced radical addition of glycosyl bromides (D-Glc, D-Gal and L-Fuc) to diethyl vinylphosphonate, or a multi-step sequence (D-GlcNAc), with subsequent coupling with morpholidate-activated nucleotide monophosphates. The in vitro inhibitory activity of UDP-Gal, GDP-Fuc and UDP-GlcNAc analogues towards glycosyltransferases (beta-1,4-Gaff, FUT3 and LgtA) was evaluated through a competition fluorescence assay and IC50 values of 40 mu M, 2 mM and 3.5 mM were obtained, respectively. (c) 2006 Elsevier Ltd. All rights reserved.
• Diastereoselective synthesis of C-glycosylphosphonates via free-radical glycosylation
  作者：Hans-Dieter Junker、Wolf-Dieter Fessner

  DOI：10.1016/s0040-4039(97)10498-1

  日期：1998.1

  A single step approach for the diastereoselective synthesis of C-glycosidic sugar phosphonates was developed by utilizing a free radical coupling to dialkyl vinylphosphonates to give the title compounds in moderate yield. The method is broadly applicable to sugars, deoxysugars, aminosugars, and oligosaccharides. (C) 1997 Elsevier Science Ltd. All rights reserved.
• Kinetic evaluation of glucose 1-phosphate analogues with a thymidylyltransferase using a continuous coupled enzyme assay
  作者：S. M. Forget、A. Jee、D. A. Smithen、R. Jagdhane、S. Anjum、S. A. Beaton、D. R. J. Palmer、R. T. Syvitski、D. L. Jakeman

  DOI：10.1039/c4ob02057j

  日期：——

  We have developed a continuous spectrophotometric kinetic assay for the detection of PP_iand have applied the assay to evaluate Cps2L, a nucleotidylyltransferase, kinetics with five synthetic substrate analogues (2–6).

  我们开发了一种连续光谱光度测定动力学方法，用于检测PPi，并已将此方法应用于评估Cps2L（一种核苷酸转移酶）与五种合成底物类似物（2-6）的动力学。
• Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis of <i>C</i> ‐linked Glycoconjugates
  作者：Weidong Shang、Sheng‐Nan Su、Rong Shi、Ze‐Dong Mou、Guo‐Qiang Yu、Xia Zhang、Dawen Niu

  DOI：10.1002/anie.202009828

  日期：2021.1.4

  We here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available, air and moisture stable precursors to glycosyl radicals. These glycosyl sulfoxides could be converted to glycosyl radicals by way of a rapid and efficient intramolecular radical substitution event. The use of this type of precursors enabled the synthesis of various complex C‐linked glycoconjugates under mild

  我们在这里报告了糖基亚砜与芳基碘化物部分相连的情况，是糖基自由基容易获得，对空气和水分稳定的前体。这些糖基亚砜可以通过快速和有效的分子内基团取代事件转化为糖基基团。使用这种类型的前体可以在温和的条件下合成各种复杂的C连接的糖缀合物。该反应可以在水性介质中进行，适合合成糖肽模拟物和碳水化合物-DNA共轭物。