N^α-acetyl-L-alanyl-N^α-methyl-3-O-[2,3,4,6-tetra-O-(3-fluorobenzoyl)-β-D-glucopyranosyl]-L-seryl-L-phenylalanine amide | 343309-05-7

• 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-acetyl-L-alanyl-N^α-methyl-3-O-[2,3,4,6-tetra-O-(3-fluorobenzoyl)-β-D-glucopyranosyl]-L-seryl-L-phenylalanine amide
• 英文别名: [(2R,3R,4S,5R,6R)-6-[(2S)-2-[[(2S)-2-acetamidopropanoyl]-methylamino]-3-[[(2S)-1-amino-1-oxo-3-phenylpropan-2-yl]amino]-3-oxopropoxy]-3,4,5-tris[(3-fluorobenzoyl)oxy]oxan-2-yl]methyl 3-fluorobenzoate
• CAS: 343309-05-7
• 化学式: C₅₂H₄₈F₄N₄O₁₄
• 分子量: 1028.97
• InChiKey: TTWQUDARYLOCSK-PPPUEOBGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  74
• 可旋转键数：
  24
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  245
• 氢给体数：
  3
• 氢受体数：
  18

反应信息

• 作为反应物：
  描述：

  N^α-acetyl-L-alanyl-N^α-methyl-3-O-[2,3,4,6-tetra-O-(3-fluorobenzoyl)-β-D-glucopyranosyl]-L-seryl-L-phenylalanine amide 在 sodium methylate 作用下， 以 甲醇 为溶剂， 生成 N^α-acetyl-L-alanyl-(2-aminoprop-2-enoyl)-L-phenylalanine amide 、 N^α-acetyl-L-alanyl-3-O-β-D-glucopyranosyl-L-seryl-L-phenylalanine amide
  参考文献：
  名称：

  Use of Fluorobenzoyl Protective Groups in Synthesis of Glycopeptides:  β-Elimination of O-Linked Carbohydrates Is Suppressed

  摘要：

  Fluorobenzoyl groups have been investigated as alternatives to acetyl and benzoyl protective groups in carbohydrate and glycopeptide synthesis. D-Glucose and lactose were protected with different fluorobenzoyl groups and then converted into glycosyl bromides in high yields (> 80% over two steps). Glycosylation of protected derivatives of serine with these donors gave 1,2-trans glycosides in good yields (similar to 60-70%) and excellent stereoselectivity without formation of ortho esters. The resulting glycosylated amino acid building blocks were then used in solid-phase synthesis of two model O-linked glycopeptides known to be unusually sensitive to beta -elimination on base-catalyzed deacylation. When either a 3-fluoro- or a 2,5-difluorobenzoyl group was used for protection of each of the two model glycopeptides the extent of beta -elimination decreased from 80% to 10% and from 50% to 0%, respectively, as compared to when using the ordinary benzoyl group. Fluorobenzoyl groups thus combine the advantages of the benzoyl group in formation of glycosidic bonds (i.e., high stereoselectivity and low levels of ortho ester formation) with the ease of removal characteristic of the acetyl group.

  DOI：

  10.1021/jo001584q
• 作为产物：
  描述：

  2,3,4,6-tetra-O-(3-fluorobenzoyl)-α-D-glucopyranosyl bromide 在 3 A molecular sieve 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 为溶剂， 反应 2.5h， 生成 N^α-acetyl-L-alanyl-N^α-methyl-3-O-[2,3,4,6-tetra-O-(3-fluorobenzoyl)-β-D-glucopyranosyl]-L-seryl-L-phenylalanine amide
  参考文献：
  名称：

  Use of Fluorobenzoyl Protective Groups in Synthesis of Glycopeptides:  β-Elimination of O-Linked Carbohydrates Is Suppressed

  摘要：

  Fluorobenzoyl groups have been investigated as alternatives to acetyl and benzoyl protective groups in carbohydrate and glycopeptide synthesis. D-Glucose and lactose were protected with different fluorobenzoyl groups and then converted into glycosyl bromides in high yields (> 80% over two steps). Glycosylation of protected derivatives of serine with these donors gave 1,2-trans glycosides in good yields (similar to 60-70%) and excellent stereoselectivity without formation of ortho esters. The resulting glycosylated amino acid building blocks were then used in solid-phase synthesis of two model O-linked glycopeptides known to be unusually sensitive to beta -elimination on base-catalyzed deacylation. When either a 3-fluoro- or a 2,5-difluorobenzoyl group was used for protection of each of the two model glycopeptides the extent of beta -elimination decreased from 80% to 10% and from 50% to 0%, respectively, as compared to when using the ordinary benzoyl group. Fluorobenzoyl groups thus combine the advantages of the benzoyl group in formation of glycosidic bonds (i.e., high stereoselectivity and low levels of ortho ester formation) with the ease of removal characteristic of the acetyl group.

  DOI：

  10.1021/jo001584q