3,4,6-tri-O-acetyl-2-deoxy-2-o-trifluoromethylbenzylideneamino-D-galactopyranosyl N-phenyl trifluoroacetimidate | 1391597-85-5

• 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: 3,4,6-tri-O-acetyl-2-deoxy-2-o-trifluoromethylbenzylideneamino-D-galactopyranosyl N-phenyl trifluoroacetimidate
• 英文别名: [(2R,3R,4R,5R,6S)-3,4-diacetyloxy-6-[N-phenyl-C-(trifluoromethyl)carbonimidoyl]oxy-5-[[2-(trifluoromethyl)phenyl]methylideneamino]oxan-2-yl]methyl acetate
• CAS: 1391597-85-5
• 化学式: C₂₈H₂₆F₆N₂O₈
• 分子量: 632.513
• InChiKey: IAZONMDBHSZROB-RXFVIIJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  44
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  122
• 氢给体数：
  0
• 氢受体数：
  16

反应信息

• 作为产物：
  描述：

  邻三氟甲基苯甲醛 在 吡啶 、 氨 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 26.5h， 生成 3,4,6-tri-O-acetyl-2-deoxy-2-o-trifluoromethylbenzylideneamino-D-galactopyranosyl N-phenyl trifluoroacetimidate 、 3,4,6-tri-O-acetyl-2-deoxy-2-o-trifluoromethylbenzylideneamino-D-galactopyranosyl N-phenyl trifluoroacetimidate
  参考文献：
  名称：

  Scalable Synthesis of Fmoc-Protected GalNAc-Threonine Amino Acid and T_N Antigen via Nickel Catalysis

  摘要：

  The highly a-selective and scalable synthesis of the Fmoc-protected GalNAc-threonine amino acid and T-N antigen in gram scale (0.51 g) is described. The challenging 1,2-cis-2-amino glycosidic bond is addressed through a coupling of threonine residues with C(2)-N-ortho-(trifluoromethyl)benzylidenamino trihaloacetimidate donors mediated by Ni(4-F-PhCN)4(OTf)(2). The desired 1,2-cis-2-amino glycoside was obtained in 66% yield (3.77 g) with a-only selectivity and subsequently transformed into the Fmoc-protected GalNAc-threonine and T-N antigen. This operationally simple procedure no longer requires utilization of the commonly used C(2)-azido donors and overcomes many of the limitations associated with the synthesis of 1,2-cis linkage.

  DOI：

  10.1021/acs.orglett.5b00780

文献信息

• Studies on the Selectivity Between Nickel-Catalyzed 1,2-<i>cis</i>-2-Amino Glycosylation of Hydroxyl Groups of Thioglycoside Acceptors with C(2)-Substituted Benzylidene <i>N</i>-Phenyl Trifluoroacetimidates and Intermolecular Aglycon Transfer of the Sulfide Group
  作者：Fei Yu、Hien M. Nguyen

  DOI：10.1021/jo301050q

  日期：2012.9.7

  glycoconjugates bearing the 1,2-cis-2-amino glycosidic linkages because the saccharide thioglycosides obtained can serve as donors for another coupling iteration. This approach streamlines selective deprotection and anomeric derivatization steps prior to the subsequent coupling event. We have developed an efficient approach for the synthesis of highly yielding and α-selective saccharide thioglycosides containing

  包含 1,2-顺式-2-氨基糖苷键的糖硫糖苷的立体选择性合成具有挑战性。除了在 1,2-顺式-2-氨基糖苷键形成中实现高α-选择性的困难之外，糖基化反应还受到异头硫化物基团从糖基受体到糖基供体的不希望的转移的阻碍。克服这些障碍将为制备带有 1,2-顺式分子的寡糖和糖缀合物铺平道路。-2-氨基糖苷键，因为获得的糖硫糖苷可以作为另一次偶联迭代的供体。这种方法在随后的偶联事件之前简化了选择性去保护和异头衍生化步骤。我们开发了一种有效的方法来合成含有 1,2-顺式-2-氨基糖苷键的高产率和 α-选择性糖硫糖苷，通过阳离子镍催化的带有 2-三氟甲基苯基苷元的硫糖苷受体的糖基化与N-苯基三氟乙酰亚胺酯供体。2-三氟甲基苯基有效地阻止异头硫化物基团从糖基受体转移到 C(2)-亚苄基供体，并且易于安装和激活。目前的方法还突出了镍催化剂在糖基受体上存在异头硫化物基团的情况下选择性活化 C(2)-亚苄基亚胺酯基团的功效。