methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-α-D-glucopyranuronate | 666238-16-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-α-D-glucopyranuronate
• CAS: 666238-16-0
• 化学式: C₂₄H₂₅NO₇
• 分子量: 439.465
• InChiKey: DYWBAEVQFHRNBO-LHQSUDNYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.71
• 重原子数：
  32.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  96.24
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-α-D-glucopyranuronate 在 palladium on activated charcoal lithium hydroxide 、 氢气 、 sodium methylate 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 乙酸乙酯 、 丙酮 为溶剂， 反应 31.0h， 生成 (2-R)-2,3,4,5-tetrahydro-5-oxo-2-furylmethyl β-D-glucopyranosiduronic acid
  参考文献：
  名称：

  Comparison of Several Glucuronate Glycosyl Donors

  摘要：

  Methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-alpha-D-glucopyranuronate (12), methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-ethoxyethylidene)]-alpha-D-glucopyranuronate (14), methyl 2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranuronate bromide (15), methyl (2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranosyl)uronate trichloroacetimidate (17), and methyl (2,3,4-tri-O-benzyl-alpha/beta-D-glucopyranosyl)uronate trichloroacetimidate (30) were synthesized and used as glycosyl donors. Glycosylation reactions of 12 with (5-R)-2,3,4,5-tetrahydro-5-trityloxymethyl-2-furanone (32) and 14,15,17 with the corresponding (5-R)-2,3,4,5-tetrahydro-5-hydroxymethyl-2-furanone (31) provided the exclusively beta-linked glucuronide 33 in 69%, 28%, 45%, and 71% yield, respectively. The coupling of donor 30 with acceptor 31 furnished the glucuronated lactone 35 in 70% yield with a surprisingly high content (20%) of the undesired alpha-linked sugar residue. The structure of 33 was proved by NMR and X-ray diffraction studies. In a model reaction a complete deprotection procedure of the glucuronic acid lactone conjugation was demonstrated.

  DOI：

  10.1081/car-120026603
• 作为产物：
  描述：

  6-O-tert-butyldimethylsilyl-[(S)-1,2-O-(1-ethoxyethylidene)]-α-D-glucopyranose 在 四丁基氯化铵 、 碳酸氢钠 sodium hypochlorite 、 TEMPO 、 乙酰溴 、 四乙基溴化铵 、 四丁基氟化铵 、 四丁基溴化铵 、 sodium hydride 、 potassium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 5.5h， 生成 methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-α-D-glucopyranuronate
  参考文献：
  名称：

  Comparison of Several Glucuronate Glycosyl Donors

  摘要：

  Methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-cyanoethylidene)]-alpha-D-glucopyranuronate (12), methyl 3,4-di-O-benzyl-[(S)-1,2-O-(1-ethoxyethylidene)]-alpha-D-glucopyranuronate (14), methyl 2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranuronate bromide (15), methyl (2-O-acetyl-3,4-di-O-benzyl-alpha-D-glucopyranosyl)uronate trichloroacetimidate (17), and methyl (2,3,4-tri-O-benzyl-alpha/beta-D-glucopyranosyl)uronate trichloroacetimidate (30) were synthesized and used as glycosyl donors. Glycosylation reactions of 12 with (5-R)-2,3,4,5-tetrahydro-5-trityloxymethyl-2-furanone (32) and 14,15,17 with the corresponding (5-R)-2,3,4,5-tetrahydro-5-hydroxymethyl-2-furanone (31) provided the exclusively beta-linked glucuronide 33 in 69%, 28%, 45%, and 71% yield, respectively. The coupling of donor 30 with acceptor 31 furnished the glucuronated lactone 35 in 70% yield with a surprisingly high content (20%) of the undesired alpha-linked sugar residue. The structure of 33 was proved by NMR and X-ray diffraction studies. In a model reaction a complete deprotection procedure of the glucuronic acid lactone conjugation was demonstrated.

  DOI：

  10.1081/car-120026603