4-nitrophenyl 2,5-anhydro-3,4-di-O-methyl-1,6-dithio-α-D-glucoseptanoside

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-nitrophenyl 2,5-anhydro-3,4-di-O-methyl-1,6-dithio-α-D-glucoseptanoside
• 英文别名: (1R,2R,5S,6S,7S)-6,7-dimethoxy-2-(4-nitrophenyl)sulfanyl-8-oxa-3-thiabicyclo[3.2.1]octane
• 化学式: C₁₄H₁₇NO₅S₂
• 分子量: 343.425
• InChiKey: QYYHHDVBPIJFOU-RKQHYHRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  2,5-anhydro-6-bromo-6-deoxy-3,4-di-O-methyl-D-glucitol 在 吡啶 、 双氧水 、 sodium methylate 、 乙酸酐 作用下， 以 1,4-二氧六环 、 甲醇 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 11.5h， 生成 4-nitrophenyl 2,5-anhydro-3,4-di-O-methyl-1,6-dithio-α-D-glucoseptanoside
  参考文献：
  名称：

  Synthesis of 4-cyano- and 4-nitrophenyl 2,5-anhydro-1,6-dithio-α-d-gluco- and -α-l-guloseptanosides carrying different substituents at C-3 and C-4

  摘要：

  Treatment of 1,6:2,5-dianhydro-3,4-di-O-methanesulfonyl-1-thio-D-glucitol in methanol with sodium hydroxided afforded 1,6:2, 5:3,4-trianhydro-1-thio-allitol, 1,4:2,5-dianhydro-6-methoxy-1-thio-D-galactitol, 1,6:2,5-dianhydro-4-O-methyl-1-thio-D-glucitol, 1,6:2,5-dianhydro-3-O-methanesulfonyl-1-thio-D-glucitol and 1,6:2,5-dianhydro-4-deoxyl-thio-D-erythro -hex-3-ulose (14) in 5, 4, 28, 5.5 and 41% yield, respectively. Formation of these derivatives can be explained via a common sulfonium intermediate. Reduction of 14 with sodium borohydride and subsequent acetylation afforded 3-O-acetyl-1,6:2,5-dianhydro-4-deoxy-1-thio-D-xylo-hexitol, the absolute configuration of which was proved by X-ray crystallography. The 1,6:2,5-dianhydro-1-thio-D-hexitol derivatives in which the free OH groups were protected by acetylation, methylation or mesylation were converted by a Pummerer reaction of their sulfoxides into the corresponding 1-O-acetyl hexoseptanose derivatives which were used as donors for the glycosidation of 4-cyano- and 4-nitrobenzenethiol, respectively. The Pummerer reaction of 1,6.2, 5-dianhydro-4-deoxy-3-O-methyl-1-thio-D-xylo-hexitol S-oxide gave, besides 1-O-acetyl-2,5-anhydro-3-deoxy-4-O-methyl-6-thio-alpha -L- (23) and 1-O-acetyl-2,5-anhydro-4-deoxy-3-O-methyl-6-thio-alpha -D-xylo-hexoseptanose (25), 1-O-acetyl-4-deoxy-2,6-thioanhydro-D-lyxo-hexopyranose, formed in a rearrangement reaction. The same rearrangement took place, when a mixture of 23 and 25 was used as donor in the glycosidation reaction with 4-cyanobenzenethiol, applying trimethylsilyl triflate as promoter. The oral antithrombotic activity of the obtained a-thioglycosides was determined in rats, using Pescador's model. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(00)00190-7

文献信息

• Synthesis of 4-cyano- and 4-nitrophenyl 2,5-anhydro-1,6-dithio-α-d-gluco- and -α-l-guloseptanosides carrying different substituents at C-3 and C-4
  作者：Éva Bozó、Sándor Boros、László Párkányi、János Kuszmann

  DOI：10.1016/s0008-6215(00)00190-7

  日期：2000.11

  Treatment of 1,6:2,5-dianhydro-3,4-di-O-methanesulfonyl-1-thio-D-glucitol in methanol with sodium hydroxided afforded 1,6:2, 5:3,4-trianhydro-1-thio-allitol, 1,4:2,5-dianhydro-6-methoxy-1-thio-D-galactitol, 1,6:2,5-dianhydro-4-O-methyl-1-thio-D-glucitol, 1,6:2,5-dianhydro-3-O-methanesulfonyl-1-thio-D-glucitol and 1,6:2,5-dianhydro-4-deoxyl-thio-D-erythro -hex-3-ulose (14) in 5, 4, 28, 5.5 and 41% yield, respectively. Formation of these derivatives can be explained via a common sulfonium intermediate. Reduction of 14 with sodium borohydride and subsequent acetylation afforded 3-O-acetyl-1,6:2,5-dianhydro-4-deoxy-1-thio-D-xylo-hexitol, the absolute configuration of which was proved by X-ray crystallography. The 1,6:2,5-dianhydro-1-thio-D-hexitol derivatives in which the free OH groups were protected by acetylation, methylation or mesylation were converted by a Pummerer reaction of their sulfoxides into the corresponding 1-O-acetyl hexoseptanose derivatives which were used as donors for the glycosidation of 4-cyano- and 4-nitrobenzenethiol, respectively. The Pummerer reaction of 1,6.2, 5-dianhydro-4-deoxy-3-O-methyl-1-thio-D-xylo-hexitol S-oxide gave, besides 1-O-acetyl-2,5-anhydro-3-deoxy-4-O-methyl-6-thio-alpha -L- (23) and 1-O-acetyl-2,5-anhydro-4-deoxy-3-O-methyl-6-thio-alpha -D-xylo-hexoseptanose (25), 1-O-acetyl-4-deoxy-2,6-thioanhydro-D-lyxo-hexopyranose, formed in a rearrangement reaction. The same rearrangement took place, when a mixture of 23 and 25 was used as donor in the glycosidation reaction with 4-cyanobenzenethiol, applying trimethylsilyl triflate as promoter. The oral antithrombotic activity of the obtained a-thioglycosides was determined in rats, using Pescador's model. (C) 2000 Elsevier Science Ltd. All rights reserved.