2-Cyano-1-methyl-3-<(phenylsulfonyl)methyl>-1,2,5,6-tetrahydropyridine | 143924-10-1

• 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: 2-Cyano-1-methyl-3-<(phenylsulfonyl)methyl>-1,2,5,6-tetrahydropyridine
• 英文别名: 5-(benzenesulfonylmethyl)-1-methyl-3,6-dihydro-2H-pyridine-6-carbonitrile
• CAS: 143924-10-1
• 化学式: C₁₄H₁₆N₂O₂S
• 分子量: 276.359
• InChiKey: KWSYNTSGOVLGRL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  69.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-Acetyl-1-methylindole trimethylsilyl enol ether 、 2-Cyano-1-methyl-3-<(phenylsulfonyl)methyl>-1,2,5,6-tetrahydropyridine 在 zinc chloride diethyl ether 作用下， 以 四氢呋喃 为溶剂， 以43%的产率得到2-Cyano-1-methyl-3-<2-<(1-methyl-2-indolyl)carbonyl>ethyl>-4-<<(1-methyl-2-indolyl)carbonyl>methyl>piperidine
  参考文献：
  名称：

  Synthesis of 20-deethylsilicine from a second-generation 2-cyano-.DELTA.3-piperidine synthon

  摘要：

  The Zn2+ ion mediated reaction of the 2-cyano-DELTA3-piperidine 9a (X = SO2C6H5) with the silyl enol ether of Na-methyl-2-acetylindole (24) led to formation of compounds 29a,b (70%) resulting from introduction of the acetylindole moiety at the exocyclic (C-7) carbon center and migration of the phenylsulfonyl group from C-7 to C-4. In contrast, reaction of 2-Cyano-DELTA3-piperidine 9b (X = CN) with 24 gave the desired C-4 acetylindole-substituted products 36a,b (1:1.3 mixture; 72% overall yield). Attempts to cyclize intermediates 36 to the tetracyclic enamine 27 were unsuccessful. Alternatively, the Zn2+-catalyzed reaction of synthons 9a and 9b with indole gave the C-7 indole-substituted aminonitriles 37a,b and 38, respectively. These intermediates were converted to DELTA2-piperidine 40 on reaction with sodium dimethyl malonate and AgBF4. Stereoselective hydrogenation of the enamine double bond in 40 furnished the required cis 3,4-disubstituted piperidine 41, which was cyclized under acidic conditions to the target molecule, 20-deethylsilicine (20).

  DOI：

  10.1021/jo00050a012
• 作为产物：
  描述：

  吡啶,3-[(苯磺酰)甲基]- 在 sodium tetrahydroborate 、 potassium carbonate 、 间氯过氧苯甲酸 、 三氟乙酸酐 、 柠檬酸 作用下， 以 甲醇 为溶剂， 反应 10.5h， 生成 2-Cyano-1-methyl-3-<(phenylsulfonyl)methyl>-1,2,5,6-tetrahydropyridine
  参考文献：
  名称：

  Synthesis of 20-deethylsilicine from a second-generation 2-cyano-.DELTA.3-piperidine synthon

  摘要：

  The Zn2+ ion mediated reaction of the 2-cyano-DELTA3-piperidine 9a (X = SO2C6H5) with the silyl enol ether of Na-methyl-2-acetylindole (24) led to formation of compounds 29a,b (70%) resulting from introduction of the acetylindole moiety at the exocyclic (C-7) carbon center and migration of the phenylsulfonyl group from C-7 to C-4. In contrast, reaction of 2-Cyano-DELTA3-piperidine 9b (X = CN) with 24 gave the desired C-4 acetylindole-substituted products 36a,b (1:1.3 mixture; 72% overall yield). Attempts to cyclize intermediates 36 to the tetracyclic enamine 27 were unsuccessful. Alternatively, the Zn2+-catalyzed reaction of synthons 9a and 9b with indole gave the C-7 indole-substituted aminonitriles 37a,b and 38, respectively. These intermediates were converted to DELTA2-piperidine 40 on reaction with sodium dimethyl malonate and AgBF4. Stereoselective hydrogenation of the enamine double bond in 40 furnished the required cis 3,4-disubstituted piperidine 41, which was cyclized under acidic conditions to the target molecule, 20-deethylsilicine (20).

  DOI：

  10.1021/jo00050a012