methyl 3,4,5-tri-O-acetyl-2,6-anhydro-D-lyxo-hex-5-enonate | 62346-09-2

• 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: methyl 3,4,5-tri-O-acetyl-2,6-anhydro-D-lyxo-hex-5-enonate
• 英文别名: methyl 2-acetoxy-3,4-di-O-acetyl-D-arabino-hex-1-enopyranuronate；2,3,4-tri-O-acetyl-2-hydroxy-D-glucuronal methyl ester；2,3,4-Tri-O-acetyl-<2-hydroxy-D-glucuronal>-methylester；Methyl 2,3,4-tri-O-acetyl-1-deoxy-D-arabino-1-ln-uronat；methyl (2S,3S,4S)-3,4,5-triacetyloxy-3,4-dihydro-2H-pyran-2-carboxylate
• CAS: 62346-09-2
• 化学式: C₁₃H₁₆O₉
• 分子量: 316.265
• InChiKey: CYRDRVVCHQYGJF-WOPDTQHZSA-N

物化性质

• 沸点：
  361.9±42.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl 3,4,5-tri-O-acetyl-2,6-anhydro-D-lyxo-hex-5-enonate 在 palladium on activated charcoal 吡啶 、 sodium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 硼烷四氢呋喃络合物 、 盐酸羟胺 、 氢气 、 silver trifluoromethanesulfonate 、 对甲苯磺酸 、 三乙胺 、 N,N'-羰基二咪唑 、 1,1,3,3-四甲基脲 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， -10.0~25.0 ℃ 、276.0 kPa 条件下， 反应 84.5h， 生成 sodium <2-(palmitoylamino)ethyl 2-acetamido-2-deoxy-β-D-mannopyranosid>uronate
  参考文献：
  名称：

  Facile Preparation and Utilization of a Novelβ-D-ManNAcA-Donor: Methyl 2-Benzoyloxyimino-1-bromo-2-deoxy-α-D-arabino-hexopyranuronate

  摘要：

  标题为β-d-ManNAcA供体的化合物，甲基2-苯甲氧基亚胺-2-脱氧-d-阿拉伯六糖糖醛酸α-溴化物9，已从d-葡萄糖醛内酯合成，七个步骤的总体产率为21%，所有中间体均能以晶体形式获得。关键化合物是2-乙酰氧基-d-葡萄糖醛酯6及其羟胺水解产物1,5-脱水-d-果糖醛酸肟7，后者通过O-苯甲酰化（→8）和光溴化进一步合成9。——作为合适的β-d-ManNAcA供体，9的利用基于两个后续反应：首先，以N封闭的2-氨基乙醇作为间隔底物，或以其他保护的糖苷的6-羟基（16）进行Koenigs-Knorr型糖苷化反应，产生β选择性达到20：1或更高；其次，通过对获得的β-糖苷进行肟还原，基本上以立体专一性的方式进行，经过N-乙酰化后，得到2-乙酰氨基-2-脱氧-β-d-甘露糖醛酸酯。——所开发的方法用于制备一些新型人工糖脂，例如（肉豆蔻酰氨基）乙基6-O-(2-乙酰氨基-2-脱氧-β-d-甘露糖吡喃糖醛酸)-α-d-葡萄糖吡喃糖苷（25）及其（硬脂酰氨基）乙基类似物（26），这些化合物正被评估作为脂质体的识别标记。

  DOI：

  10.1246/bcsj.67.1130
• 作为产物：
  描述：

  D-GLUCURONIDEMETHYLESTERD-葡糖苷酸甲酯 在 四丁基溴化铵 、 氢溴酸 、 溶剂黄146 、 二甲胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 methyl 3,4,5-tri-O-acetyl-2,6-anhydro-D-lyxo-hex-5-enonate
  参考文献：
  名称：

  Glucuronic acid-based ulosyl donors for introducing α-d-GlcA and β-d-ManA units

  摘要：

  Practical protocols are described for a five-step conversion Of D-glucuronolactone into Ot-D-arabino-2-ketoglueuronyl bromides, which due to their alpha-selective or beta-specific glycosidation, and gluco- or manno-specific carbonyl reductions of the glucurono2-ulosides formed, are expedient indirect donor substrates for the efficient introduction Of alpha-D-GIcA or beta-D-ManA residues. (c) 2007 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2007.05.008

文献信息

• Extended scaffold glucuronides: <i>en route</i> to the universal synthesis of <i>O</i>-aryl glucuronide prodrugs
  作者：Raoul Walther、Morten T. Jarlstad Olesen、Alexander N. Zelikin

  DOI：10.1039/c9ob01384a

  日期：——

  We demonstrate that an extended scaffold based on a self-immolative linker (SIL) enables the universal production of O-aryl glucuronide prodrugs: high yield glucuronidation is performed on a precursor substrate (SIL) and the subsequent drug conjugation proceeds via less challenging chemical reactions.

  我们证明了基于自消灭性接头（SIL）的扩展支架可以实现O-芳基葡糖醛酸前药的普遍生产：在前体底物（SIL）上进行高产率的葡糖醛酸化，随后的药物偶联反应通过更具挑战性的化学反应进行。
• A convenient and efficient method for the synthesis of 2-hydroxy glycals
  作者：Bin Qian、Qi-Dong You

  DOI：10.1016/j.tetlet.2012.05.016

  日期：2012.7

  A convenient and efficient method for preparing 2-hydroxy glycals was developed from thioglycosides by using 1,4-dioxane–bromine complex/DMAP as an efficient promoter with good yield (61–85%). In this synthetic method, a wide range of sugar thioglycosides could be used as substrates.

  通过使用1,4-二恶烷-溴复合物/ DMAP作为高效的促进剂，并具有良好的产率（61-85％），从硫代糖苷开发了一种方便高效的制备2-羟基乙二醇的方法。在这种合成方法中，各种各样的糖硫糖苷可以用作底物。
• Polymethylhydrosiloxane (PMHS): A Convenient Option for Synthetic Applications of the Iodine/Silane Combined Reagent - Straightforward Entries to 2-Hydroxyglycals and Useful Building-Blocks of Glucuronic Acid and Glucosamine
  作者：Maddalena Giordano、Alfonso Iadonisi

  DOI：10.1002/ejoc.201201084

  日期：2013.1

  Polymethylhydrosiloxane (PMHS) proved to be a practically convenient alternative to triethylsilane in a large set of synthetic elaborations entailing the quick generation of glycosyl iodides with a iodine/silane combined reagent. In addition, the scope of this combined reagent was expanded to the especially fast generation of 2-acetoxyglycals, and the rapid synthesis of useful building-blocks of D-glucuronic

  在大量合成过程中，聚甲基氢硅氧烷 (PMHS) 被证明是三乙基硅烷的实用替代品，这些合成过程需要使用碘/硅烷组合试剂快速生成糖基碘。此外，该组合试剂的范围扩大到特别快速生成 2-乙酰氧基糖醛，以及快速合成 D-葡萄糖醛酸和 D-葡萄糖胺的有用结构单元。所有合成目标都在特别短的时间内通过一锅法或通过实验序列获得，无需费力的中间体色谱纯化。
• Synthesis of a 2-Acetamido-2-deoxy-β-D-mannuronic Acid-Containing Artificial Glycolipid Corresponding to the Repeating Unit of a Teichuronic Acid from<i>Micrococcus luteus</i>
  作者：Yumiko Osa、Eisuke Kaji、Keiko Takahashi、Motoko Hirooka、Shonosuke Zen、Frieder W. Lichtenthaler

  DOI：10.1246/cl.1993.1567

  日期：1993.9

  A new type of artificial glycolipid constituted with 2-acetamido-2-deoxy-β-D-mannuronic acid was synthesized utilizing a readily accessible building block, methyl 2-(benzoyloxy)iminoglycosuronate as the glycosyl donor. Stereocontrolled β-glycosidation of the donor was as smoothly effected as the subsequent stereospecific reduction of (benzoyloxy)imino function. After anomeric activation, attachment of the spacer (2-aminoethanol)-linked stearic acid and final deblocking gave the designed glycolipid in good overall yield.

  我们利用一种容易获得的结构单元--2-（苯甲酰氧基）亚氨基糖苷酸甲酯作为糖基供体，合成了一种由 2-乙酰氨基-2-脱氧-β-D-甘露糖酸构成的新型人工糖脂。供体的立体定向 β-糖苷化与随后的（苯甲酰氧基）亚氨基功能的立体定向还原一样顺利。经过异构活化、连接间隔物（2-氨基乙醇）-连接硬脂酸和最终解锁，就得到了所设计的糖脂，而且总收率很高。
• A convenient new synthesis of quaternary ammonium glucuronides of drug molecules
  作者：Lisa Iddon、Ryan A. Bragg、John R. Harding、Andrew V. Stachulski

  DOI：10.1016/j.tet.2009.10.113

  日期：2010.1

  N-Glucuronides, of various Structural types, are frequently encountered as drug metabolites. Efficient chemical synthesis of these compounds, both as analytical standards and for toxicological investigation, is therefore an important goal. Earlier syntheses of N+-glucuronides of aliphatic tertiary amine drugs involved direct reaction of the drug molecule with a bromosugar, but yields were generally low and of poor reproducibility, with many by-products. In addition the final products were often of low stability, hindering effective isolation and purification. We now report that a stable, readily prepared glucuronic acid hemiacetal is a reliable precursor for metabolites of this type and give three pharmaceutically relevant examples. We report further on the stability of the final metabolites and the conditions required for their isolation and purification. (C) 2009 Elsevier Ltd. All rights reserved.