N^α-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl)-L-threonine pentafluorophenyl ester | 141462-10-4

• 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: N^α-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl)-L-threonine pentafluorophenyl ester
• 英文别名: (2,3,4,5,6-pentafluorophenyl) (2S,3R)-3-[(2S,3R,4R,5R,6R)-4,5-diacetyloxy-6-(acetyloxymethyl)-3-azidooxan-2-yl]oxy-2-(9H-fluoren-9-ylmethoxycarbonylamino)butanoate
• CAS: 141462-10-4
• 化学式: C₃₇H₃₃F₅N₄O₁₂
• 分子量: 820.681
• InChiKey: UWPFWJBQXFJMMM-BDIDVHOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  58
• 可旋转键数：
  18
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  176
• 氢给体数：
  1
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  N^α-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl)-L-threonine pentafluorophenyl ester 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 2.5h， 生成 Ac-Pro-Thr-Thr-Thr(α-D-GalNAc)-Pro-Leu-Lys-NH2
  参考文献：
  名称：

  粘蛋白样糖肽的平行固相合成

  摘要：

  摘要糖肽Ac-Pro-Thr（α-d -GalNAc）-Thr（α-d -GalNAc）-Thr（α-d-GalNAc）-Pro-Leu-Lys-NH 2（1）具有三个特征通过固相合成制备了连续的O-糖基化的Thr残基并模拟了一部分粘蛋白2。还合成了七个相关的，部分糖基化的肽（2-8）。这组分子允许对合成方案进行系统分析。Nα-（9-氟烯基甲氧羰基）-O-（3,4,6-三-O-乙酰基-2-叠氮基-2-脱氧-α-d-吡喃半乳糖基）-1-苏氨酸五氟苯基酯[Fmoc-1-Thr （Ac 3-α-d -GalN 3）-OPfp]被用作构建基，当以相对较低的摩尔过量（约1.5当量）使用N，N-二甲基甲酰胺（DMF）作为化合物时，可以有效地偶联。溶剂。为了将叠氮基团转化为N-乙酰基官能团，与用二硫苏糖醇（DTT）还原然后进行N-乙酰化的两步程序相比，用硫代乙酸直接处理更为可取。通过在甲醇中的甲醇钠（10-15

  DOI：

  10.1016/j.carres.2005.05.023
• 作为产物：
  描述：

  3,4,6-tri-O-acetyl-2-azido-2-deoxy-D-galactopyranosyl nitrate 在 四乙基氯化铵 、 silver perchlorate 、 silver carbonate 、 lithium bromide 作用下， 以 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 81.5h， 生成 N^α-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-D-galactopyranosyl)-L-threonine pentafluorophenyl ester
  参考文献：
  名称：

  Syntheses of TN building blocks Nα-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-galactopyranosyl)-l-serine/l-threonine pentafluorophenyl esters: comparison of protocols and elucidation of side reactions

  摘要：

  T-N antigen building blocks N-alpha-(9-fluorenylmethoxycarbonyl)-O-(3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-galactopyranosyl)-L-serine/L-threonine pentafluorophenyl ester [Fmoc-L-Ser/L-Thr(Ac-3-alpha-D-GalN(3))-OPfP, 13/14] have been synthesized by two different routes, which have been compared. Overall isolated yields [three or four chemical steps, and minimal intermediary purification steps] of enantiopure 13 and 14 were 5-18% and 6-10%, respectively, based on 3,4,6-tri-O-acetyl-D-galactal (1). A byproduct of the initial azidonitration reaction of the synthetic sequence, that is, N-acetyl-3,4,6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-galactopyranosylamine (5), has been characterized by X-ray crystallography, and shown by H-1 NMR spectroscopy to form complexes with lithium bromide, lithium iodide, or sodium iodide in acetonitrile-d(3). Intermediates 3,4,6-tri-O-acetyl-2-azido2-deoxy-alpha-D-galactopyranosyl bromide (6) and 3,4,6-tri-O-acetyl-2-azido-2-deoxy-beta-D-galactopyranosyl chloride (7) were used to glycosylate N-alpha-(9-fluorenylmethoxycarbonyl)-L-serine/L-threonine pentafluorophenyl esters [Fmoc-L-Ser/L-Thr-OPfp, 11/12]. Previously undescribed low-level dehydration side reactions were observed at this stage; the unwanted byproducts were easily removed by column chromatography. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2005.02.029