methyl 5-cyano-6-(2-methoxycarbonylethylsulfanyl)-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate | 501910-23-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: methyl 5-cyano-6-(2-methoxycarbonylethylsulfanyl)-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate
• 英文别名: Methyl 5-cyano-6-(3-methoxy-3-oxopropyl)sulfanyl-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate
• CAS: 501910-23-2
• 化学式: C₁₉H₂₀N₂O₄S
• 分子量: 372.445
• InChiKey: PBFNOLCRJBUMGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  26
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  114
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 5-cyano-6-(2-methoxycarbonylethylsulfanyl)-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate 在 amano acylase from Aspergillus mellus 、 水 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 异丙醚 、 水 为溶剂， 反应 97.5h， 生成 (-)-methyl 5-cyano-2-methyl-6-methylsulfanyl-4-phenyl-1,4-dihydropyridine-3-carboxylate
  参考文献：
  名称：

  Effective Method of Lipase-Catalyzed Enantioresolution of 6-Alkylsulfanyl-1,4-dihydropyridines

  摘要：

  A series of 6-alkylsulfanyl-1,4-dihydropyridines (+/-)-2 bearing a methoxycarbonylethyl group as a mild easily removable protecting group at S atom have been prepared by alkylation of 6-thioxo-1,4-dihydropyridines 1 with methyl bromopropionate. Candida antarctica lipase B (Novozyme 435 (R), CAL-B) - and Amano Acylase (Aspergillus mellus)-catalyzed kinetic resolution has been investigated in water-saturated diisopropyl ether (IPE) at 25 and 45 degrees C. After acrylic acid methyl ester as leaving group cleavage and alkylation of formed enantioenriched 1,4-dihydropyridine-6-thiolates (-)-4 and (+)-4, optically active 1,4-dihydropyridines (-)-2, (+)-2, (-)-5 and (+)-5 were obtained in 85-99% enantiomeric excess. The experiments present the 6-(methoxycarbonylethyl)sulfanyl group as an essentially new enzymatically labile (activating) group. The ester group being 6 bonds remote from the chiral center undergoes easy enzymatic hydrolysis and could be used for kinetic resolution of racemic 1,4-DHPs. This developed method offers access to mild optically active nucleophilic tiolates, which could be easily derivatized with electrophilic reagents.

  DOI：

  10.3987/com-13-12839
• 作为产物：
  描述：

  苯甲醛 在 哌啶 、 盐酸 作用下， 以 甲醇 、 乙醇 为溶剂， 反应 1.17h， 生成 methyl 5-cyano-6-(2-methoxycarbonylethylsulfanyl)-2-methyl-4-phenyl-1,4-dihydropyridine-3-carboxylate
  参考文献：
  名称：

  Effective Method of Lipase-Catalyzed Enantioresolution of 6-Alkylsulfanyl-1,4-dihydropyridines

  摘要：

  A series of 6-alkylsulfanyl-1,4-dihydropyridines (+/-)-2 bearing a methoxycarbonylethyl group as a mild easily removable protecting group at S atom have been prepared by alkylation of 6-thioxo-1,4-dihydropyridines 1 with methyl bromopropionate. Candida antarctica lipase B (Novozyme 435 (R), CAL-B) - and Amano Acylase (Aspergillus mellus)-catalyzed kinetic resolution has been investigated in water-saturated diisopropyl ether (IPE) at 25 and 45 degrees C. After acrylic acid methyl ester as leaving group cleavage and alkylation of formed enantioenriched 1,4-dihydropyridine-6-thiolates (-)-4 and (+)-4, optically active 1,4-dihydropyridines (-)-2, (+)-2, (-)-5 and (+)-5 were obtained in 85-99% enantiomeric excess. The experiments present the 6-(methoxycarbonylethyl)sulfanyl group as an essentially new enzymatically labile (activating) group. The ester group being 6 bonds remote from the chiral center undergoes easy enzymatic hydrolysis and could be used for kinetic resolution of racemic 1,4-DHPs. This developed method offers access to mild optically active nucleophilic tiolates, which could be easily derivatized with electrophilic reagents.

  DOI：

  10.3987/com-13-12839