methyl (1-adamantyl 5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-non-2-ylopyranosid)onate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (1-adamantyl 5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-non-2-ylopyranosid)onate
• 英文别名: methyl (3aR,4R,6R,7aS)-6-(1-adamantylsulfanyl)-2-oxo-4-[(1R,2R)-1,2,3-trihydroxypropyl]-3a,4,7,7a-tetrahydro-3H-pyrano[3,4-d][1,3]oxazole-6-carboxylate
• 化学式: C₂₁H₃₁NO₈S
• 分子量: 457.545
• InChiKey: SBZWCGRNJOYTAJ-KWCLAHEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  31
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  160
• 氢给体数：
  4
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl (1-adamantyl 5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-non-2-ylopyranosid)onate 在 吡啶 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 3.5h， 生成 methyl (octyl 5-acetamido-7,8,9-tri-O-acetyl-5-N,4-O-carbonyl-3,5-dideoxy-D-glycero-α-D-galactonon-2-ulopyranoside)onate
  参考文献：
  名称：

  侧链构象和构型对糖基供体反应性和选择性的影响，如 7 位唾液酸供体差向异构所示

  摘要：

  合成了两个 N-乙酰基 4O,5N-恶唑烷酮保护的 7 位唾液酸硫糖苷差向异构体，并比较了它们在糖基化反应中的反应性和立体选择性。结果表明，天然 7S 供体比非天然 7R 异构体更具反应性和 α 选择性。反应性的差异归因于侧链构象，特别是 O7 与异头中心的接近程度。在天然 7S 异构体中，O7 比在其非天然 7R 差向异构体中更靠近异头异构体中心，因此能够更好地支持反应位点处的初始正电荷。选择性的差异也归因于侧构象，在非自然的 7R 系列中，它垂直放置在供体的 α 面上方，因此比 7S 系列更大程度地屏蔽它。这些观察结果与从葡萄糖和半乳糖系列中的构象锁定模型得出的侧链构象对反应性和选择性影响的早期结论一致，并证实了这些影响主要是立体电子而不是扭转的建议。讨论了侧链构象作为远程保护基团影响糖基化立体选择性的一个因素以及作为糖苷键形成和水解酶促过程中的控制元素的可能相关性。对唾液酸糖苷中异头

  DOI：

  10.1021/ja410683y
• 作为产物：
  描述：

  methyl (2R,4S,5R,6R)-2-(1-adamantylsulfanyl)-4-hydroxy-5-[(2-methylpropan-2-yl)oxycarbonylamino]-6-[(1R,2R)-1,2,3-trihydroxypropyl]oxane-2-carboxylate 在 盐酸 、 碳酸氢钠 作用下， 以 四氢呋喃 、 乙醚 、 水 、 乙腈 为溶剂， 反应 3.5h， 生成 methyl (1-adamantyl 5-N,4-O-carbonyl-3,5-dideoxy-2-thio-D-glycero-β-D-galacto-non-2-ylopyranosid)onate
  参考文献：
  名称：

  Exploration of the Oxazolidinthione Protecting System for the Synthesis of Sialic Acid Glycosides

  摘要：

  An N-acetyl oxazolidinthione-protected sialyl thioglycoside was synthesized and its use as a sialyl donor studied. The strongly electron-withdrawing nature of the oxazolidinthione moiety is such that activation could not be achieved at -78 degrees C. Couplings were therefore conducted at the lowest convenient temperature (-50 degrees C). Glycosides were formed in good yield but in two out of three cases studied selectivities were lower than those seen with the corresponding N-acetyl oxazolidinone-protected donor. The resulting N-acetyl oxazolidinthione-protected disaccharides were converted to the corresponding N-acetyl oxazolidinones by treatment with N-iodosuccinimide and triflic acid in the presence of water at 0 degrees C.

  DOI：

  10.1080/07328303.2013.804081

文献信息

• α-Selective Sialylations at −78 °C in Nitrile Solvents with a 1-Adamantanyl Thiosialoside
  作者：David Crich、Wenju Li

  DOI：10.1021/jo7012912

  日期：2007.9.1

  [GRAPHICS]Novel 1-adamantanylthio sialosides were synthesized and coupled to acceptors under NIS/TfOH promotion conditions. These donors showed higher reactivity than the phenylthio sialosides and could be activated by NIS/TfOH in nitrile solvents at -78 degrees C to afford improved alpha-sialylations. With the N-acetyl-5-N,4-O-oxazolidinone-protected 1-adamantanylthio sialyl donor high alpha-selectivities could be achieved in the sialylations of both primary and sterically hindered secondary acceptors, including the important galactose 3-OH acceptors.