4-C-acetoxymethyl-3,5-di-O-acetyl-1,2-O-(1-methylethylidene)-β-L-threo-pentofuranose | 946079-95-4

• 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: 4-C-acetoxymethyl-3,5-di-O-acetyl-1,2-O-(1-methylethylidene)-β-L-threo-pentofuranose
• 英文别名: 4-C-acetoxymethyl-3,5-di-O-acetyl-1,2-O-isopropylidene-β-L-threo-pentofuranose
• CAS: 946079-95-4
• 化学式: C₁₅H₂₂O₉
• 分子量: 346.334
• InChiKey: SDKPMSHESIGIEO-UPJWGTAASA-N

物化性质

• 熔点：
  45-46 °C
• 沸点：
  402.5±45.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.29
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  106.59
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  4-C-acetoxymethyl-3,5-di-O-acetyl-1,2-O-(1-methylethylidene)-β-L-threo-pentofuranose 在 甲醇 、 N,O-双三甲硅基乙酰胺 、 硫酸 、 氨 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 反应 11.0h， 生成 1-(4'-C-hydroxymethyl-β-D-xylofuranosyl)thymine
  参考文献：
  名称：

  Biocatalytic Deacylation Studies on Tetra-O-acyl-β-d-xylofuranosyl Nucleosides: Synthesis of xylo-LNA Monomers

  摘要：

  A Novozyme-435 catalytic methodology has been developed for selective deacylation of one of the acyloxy functions involving a primary -OH group over the other acyloxy functions involving primary and secondary -OH groups in 4'-C-acyloxymethyl-2',3',5'-tri-O-acyl-beta-D-xylofuranosyl nucleosides. Optimization of the biocatalytic reaction revealed that tetra-O-butanoyl-beta-D-xylofuranosyl nucleosides are the best substrates for the enzyme. The possibility of acyl migration during enzymatic deacylation reactions has been ruled out by carrying out biocatalytic deacylation reactions on mixed esters of 4'-C-hydroxymethyl-2',3',5'-tri-O-acetyl-beta-D-xylofuranosyl nucleosides. The developed methodology has been used for the efficient synthesis of xylo-LNA monomers T, U, A, and C in good yields.

  DOI：

  10.1021/jo201060t
• 作为产物：
  描述：

  4-(羟甲基)-1,2-O-异丙亚基-3-O-苄基-beta-L-苏式戊呋喃糖 在 palladium on activated charcoal 4-二甲氨基吡啶 、 氢气 、 potassium carbonate 作用下， 以 甲醇 、 乙酸乙酯 为溶剂， 生成 4-C-acetoxymethyl-3,5-di-O-acetyl-1,2-O-(1-methylethylidene)-β-L-threo-pentofuranose
  参考文献：
  名称：

  Deacylation studies on furanose triesters using an immobilized lipase: Synthesis of a key precursor for bicyclonucleosides

  摘要：

  Lipozyme® TL IM固定在硅胶上作为催化剂，能够高度选择性和高效地将4-C-酰氧甲基-3,5-二-O-酰基-1,2-O-(1-甲基亚乙基)-β-L-苏式-戊呋喃糖转化为3,5-二-O-酰基-4-C-羟甲基-1,2-O-(1-甲基亚乙基)-α-D-木式-戊呋喃糖。

  DOI：

  10.1039/b618426j

文献信息

• Selective biocatalytic deacylation studies on furanose triesters: a novel and efficient approach towards bicyclonucleosides
  作者：Ashok K. Prasad、Neerja Kalra、Yogesh Yadav、Sunil K. Singh、Sunil K. Sharma、Shamkant Patkar、Lene Lange、Carl E. Olsen、Jesper Wengel、Virinder S. Parmar

  DOI：10.1039/b711455a

  日期：——

  the deacylation of 4-C-acyloxymethyl-3,5-di-O-acyl-1,2-O-(1-methylethylidene)-beta-L-threo-pentofura nose to form 3,5-di-O-acyl-4-C-hydroxymethyl-1,2-O-(1-methylethylidene)-alpha-D-xylo-pentofura nose in a highly selective and efficient manner. The rate of lipase-catalyzed deacylation of tributanoyl furanose is 2.3 times faster than the rate of deacylation of the triacetyl furanose derivative. In order

  Lipozyme TL IM催化4-C-酰氧基甲基-3,5-二-O-酰基-1,2-O-（1-甲基乙叉基）-β-L-苏-五氟呋喃鼻的脱酰基反应以形成3,5-di -O-酰基-4-C-羟甲基-1,2-O-（1-甲基亚乙基）-α-D-木基-五氟呋喃鼻具有高度选择性和高效的方式。脂肪酶催化的三丁酰呋喃糖的脱酰速率比三乙酰基呋喃糖衍生物的脱酰速率快2.3倍。为了确认脂肪酶催化的脱酰产物的结构，将其转化为双环糖衍生物，其可用于合成在开发新型反义和反义寡核苷酸中重要的双环核苷。进一步，
• Novel Selective Biocatalytic Deacylation Studies on Key Precursors for Bicyclonucleosides
  作者：Ashok K. Prasad、Sunil K. Singh、Neerja Kalra、Nidhi Singhal、Jesper Wengel、Virinder S. Parmar

  DOI：10.1080/15257770701544302

  日期：2007.11.26

  Immobilized Candida antarctica lipase and Thermomyces lanuginosus lipase catalyze the deacylation of precursors of LNA analogs, 4'-C-acyloxymethyl-2',3',5'-tri-O-acyl-beta-L-threopentofuranosylthymine and 4-C-acyloxymethyl-3,5-di-O-acyl-1,2-O-(1-methylethylidene)-beta-L-threopentofuranose, respectively in a highly selective and efficient manner.
• Biocatalytic Route to Sugar-PEG-Based Polymers for Drug Delivery Applications
  作者：Sumati Bhatia、Andreas Mohr、Divya Mathur、Virinder S. Parmar、Rainer Haag、Ashok K. Prasad

  DOI：10.1021/bm200647a

  日期：2011.10.10

  Sugar-PEG-based polymers were synthesized by enzymatic copolymerization of 4-C-hydroxymethyl-1,2-O-isopropylidene-beta-L-threo-pentofuranose/4-C-hydroxymethyl-1,2-O-benzylidene-beta-L-threo-pentofuranose/4-C-hydroxymethyl-1,2-O-isopropylidene-3-O-pentyl-beta-L-threo-pentofuranose with PEG-600 dimethylester using Novozyme-435 (Candida antarctica lipase immobilized on polyacrylate). Carbohydrate monomers were obtained by the multistep synthesis starting from diacetone-D-glucose and PEG-600 dimethyl ester, which was in turn obtained by the esterification of the commercially available PEG-600 diacid. Aggregation studies on the copolymers revealed that in aqueous solution those polymers bearing the hydrophobic pentyl/benzylidene moiety spontaneously self-assembled into supramolecular aggregates. The critical aggregation concentration (CAC) of polymers was determined by surface tension measurements, and the precise size of the aggregates was obtained by dynamic light scattering. The polymeric aggregates were further explored for their drug encapsulation properties in buffered aqueous solution of pH 7.4 (37 degrees C) using nile red as a hydrophobic model compound by means of UV/vis and fluorescence spectroscopy. There was no significant encapsulation in polymer synthesized from 4-C-hydroxymethyl-1,2-O-isopropylidene-beta-L-threo-pentofuranose because this sugar monomer does not contain a big hydrophobic moiety as the pentyl or the benzylidene moiety. Nile red release study was performed at pH 5.0 and 7.4 using fluorescence spectroscopy. The release of nile red from the polymer bearing benzylidene moiety and pentyl moiety was observed with a half life of 3.4 and 2.0 h, respectively at pH 5.0, whereas no release was found at pH 7.4.