methyl 3-cyano-6-methyl-4-phenyl-2-sulfanylidene-3,4-dihydro-1H-pyridine-5-carboxylate | 95613-35-7

• 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 3-cyano-6-methyl-4-phenyl-2-sulfanylidene-3,4-dihydro-1H-pyridine-5-carboxylate
• CAS: 95613-35-7
• 化学式: C₁₅H₁₄N₂O₂S
• 分子量: 286.354
• InChiKey: NBXREKQAFWIELH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.29
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  62.12
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 3-cyano-6-methyl-4-phenyl-2-sulfanylidene-3,4-dihydro-1H-pyridine-5-carboxylate 在 哌啶 、 lipase from Candida antarctica 、 水 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 异丙醚 、 水 为溶剂， 反应 20.67h， 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：

  3-methoxycarbonyl-5-cyano-2-methyl-4-phenyl-1,4-dihydropyridine-6-thiol piperidinium salt 、 盐酸 生成 methyl 3-cyano-6-methyl-4-phenyl-2-sulfanylidene-3,4-dihydro-1H-pyridine-5-carboxylate
  参考文献：
  名称：

  KRAUZE, A. A.;PELCHER, YU. EH.;KALME, Z. A.;DUBUR, G. YA., XIMIYA GETEROTSIKL. SOEDIN., 1984, N 12, 1694

  摘要：

  DOI：

文献信息

• Synthesis and enantioselective lipase-catalyzed kinetic resolution of methyl 6-(methoxycarbonyl-methyl)sulfanyl-1,4-dihydropyridine-3-carboxylates
  作者：Z. Andzans、A. Krauze、I. Adlere、L. Krasnova、G. Duburs

  DOI：10.1007/s10593-013-1263-8

  日期：2013.6

  A series of methyl 6-(methoxycarbonylmethyl)sulfanyl-1,4-dihydropyridine-3-carboxylates as more lipophilic derivatives of biologically active 6-methylsulfanyl-1,4-dihydropyridine-3-carboxylic acid esters has been prepared by alkylation of 6-thioxo-1,4-dihydropyridines with methyl bromoacetate. The kinetic resolution catalyzed by Candida antarctica lipase B (Novozym 435®) has been investigated; the

  已经通过6-烷基的烷基化制备了一系列6-（甲氧基羰甲基）硫烷基-1,4-二氢吡啶-3-羧酸甲酯，作为具有生物活性的6-甲基硫烷基-1,4-二氢吡啶-3-羧酸酯的亲脂性衍生物。 thioxo-1,4-dihydropyridines与溴乙酸甲酯。通过南极假丝酵母脂肪酶B（的Novozym 435催化的动力学拆分®）已经研究; 目标产物的对映体过量达到70％。实验表明6-（甲氧羰基甲基）硫烷基是本质上是新的活化基团，其通过手性中心的五个键被除去，易于酶水解，可用于外消旋1,4-二氢吡啶的动力学拆分。
• Synthesis Of 6- Alkoxycarbonylmethylsulfanyl-5-Cyano-2- Methyl-4-Phenyl-1,4-Dihydropyridine-3-Carboxylates
  作者：A. Krauze、L. Sīle、L. Chernova、Z. Andzans、G. Duburs

  DOI：10.1515/hc.2009.15.4.297

  日期：2009.1

  6-Alkoxycarbonylmethylsulfanyl-5-cyano-2-methyl-4-phenyl 1,4-dihydropyridine-3-carboxylates 3 as a more lipophilic derivatives of the biologically active 6-methylsulfanyl-1,4-DHP-3-carboxylates 2 have been prepared by the alkylation of 1,4-dihydropyridine-6-thiolates 1 with alkyl bromoacetates. Reactivity of 2 with KOH/H2O was investigated.