methyl 3-O-benzyl-α-L-idopyranoside uronic acid | 1258005-79-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3-O-benzyl-α-L-idopyranoside uronic acid
• 英文别名: methyl 3-O-benzyl-α-L-iduronic acid pyranoside；(2R,3S,4S,5R,6R)-3,5-dihydroxy-6-methoxy-4-phenylmethoxyoxane-2-carboxylic acid
• CAS: 1258005-79-6
• 化学式: C₁₄H₁₈O₇
• 分子量: 298.293
• InChiKey: LZSFZOWBVLWHIH-SVPLCASGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  105
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 3-O-benzyl-α-L-idopyranoside uronic acid 在 吡啶 、 pyridine-SO3 complex 作用下， 反应 2.0h， 以45%的产率得到methyl 3-O-benzyl-2-O-sulfonato-α-L-iduronic acid pyranoside disodium salt
  参考文献：
  名称：

  Free Energy Landscapes of Iduronic Acid and Related Monosaccharides

  摘要：

  The pyranose ring of L-iduronic acid (IdoA), a major constituent of the anticoagulant heparin, is an equilibrium of multiple ring puckers that have evaded quantification by experiment or computation. In order to resolve this enigma, we have calculated the free energy landscape of IdoA and two related monosaccharides from extensive microsecond simulations. After establishing that the simulated puckers had reached equilibrium, hypotheses were confirmed that (a) IdoA C-1(4)- and C-4(1)-chair conformations exchange on the microsecond time scale, (b) C5 epimerization leads to a C-4(1)-chair, and (c) IdoA 2-O-sulfation (IdoA2S) stabilizes the C-1(4) conformer. The IdoA and IdoA2S C-1(4) conformers were isoenergetic and computed to be 0.9 and 2.6 kcal mol(-1) lower in free energy than their respective C-4(1)-chair conformations. The simulations also predicted that the IdoA S-2(o)-skew-boat was less populated than previously thought. Novel chemical synthesis and ultra-high-field NMR supported these observations, but slight discrepancies in observed and predicted NMR vicinal couplings implied that the simulation overestimated the population of the IdoA C-4(1)-chair with respect to (1)C(4-)chair due to small force field inaccuracies that only manifest in long simulations. These free-energy calculations drive improvements in computational methods and provide a novel route to carbohydrate mimetic biomaterials and pharmaceuticals.

  DOI：

  10.1021/ja1054143
• 作为产物：
  描述：

  methyl (methyl 2-O-benzoyl-3-O-benzyl-α-L-idopyranosid)uronate 在 水 、 potassium hydroxide 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 2.0h， 以63%的产率得到methyl 3-O-benzyl-α-L-idopyranoside uronic acid
  参考文献：
  名称：

  通过 [3.2.1] 和 [2.2.2] l-艾杜糖醛酸内酯从大量葡萄糖衍生的氰醇水解合成 l-艾杜糖醛酸衍生物：一种可逆构象转换的超解除/重新武装内酯途径制备肝素二糖

  摘要：

  l- Idofuranoside 氰醇1被大规模转化为l- IdoA 甲基吡喃糖苷和呋喃糖苷的混合物，它们会聚以提供生成双环 [3.2.1] 或 [2.2.2] l-艾杜糖醛酸内酯的短 2 步路线。前者是通过 3-OBn l -IdoA 的 100 g 规模合成获得的。这种混合物的两步转化提供了新的[2.2.2] l-艾杜糖苷酸内酯的纯端基异构体。[3.2.1] 和 [2.2.2] 内酯均转化为 GlcN-IdoA 肝素前体二糖。[2.2.2] 内酯可实现从1开始的可扩展 3 步路线一种新型的高度解除武装的O-4艾杜糖苷酸，它是一种有效的受体与葡萄糖叠氮化物硫糖苷供体。由此产生的新的艾杜糖[2.2.2] 内酯二糖很容易通过温和的甲醇分解来提供 GlcN-IdoA 苯硫基二糖供体，从而阻止了它们在组装肝素和硫酸乙酰肝素样寡糖方面的既定用途。[2.2.2] 内酯化作为超解除艾杜糖醛酸成分的构象转换，可通过内酯开环逆转。此外，分离的

  DOI：

  10.1021/jo502776f