4--3-(3-indolylmethyl)-1-methyl-1,4,5,6-tetrahydropyridine | 137710-68-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 4--3-(3-indolylmethyl)-1-methyl-1,4,5,6-tetrahydropyridine
• 英文别名: dimethyl 2-[5-(1H-indol-3-ylmethyl)-1-methyl-3,4-dihydro-2H-pyridin-4-yl]propanedioate
• CAS: 137710-68-0
• 化学式: C₂₀H₂₄N₂O₄
• 分子量: 356.422
• InChiKey: JKHKPVQZKDUDTD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.51
• 重原子数：
  26.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  71.63
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  4--3-(3-indolylmethyl)-1-methyl-1,4,5,6-tetrahydropyridine 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 5.0h， 以92%的产率得到cis-4--3-(3-indolylmethyl)-1-methylpiperidine
  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：

  2-Cyano-1-methyl-3-(3-indolylmethyl)-1,2,5,6-tetrahydropyridine 、 丙二酸二甲酯 在 silver tetrafluoroborate 、 sodium hydride 作用下， 生成 4--3-(3-indolylmethyl)-1-methyl-1,4,5,6-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

文献信息

• “Tandem” reactivity of 2-cyano-Δ3-piperideines: a new approach to the synthesis of ervatamine type indole alkaloids.
  作者：Jean-Luc Bettiol、Ildiko Buck、Henri-Phillippe Husson、David S. Grierson、Anna Diez、Mario Rubiralta

  DOI：10.1016/s0040-4039(00)92400-6

  日期：1991.9

  Laboratory of Organic Chemistry, Faculty of Pharmacy, University of Barcelona, 08028-Barcelona, Spain. The synthesis of 20-dethylsilicine in four steps, from a 2-cyano-Δ3-piperideine substituted at C-3 by a CH2OAc group, is reported.

  巴塞罗那大学药学院有机化学实验室，西班牙巴塞罗那08028。20 dethylsilicine的四个步骤合成，从2-氰基Δ 3 -piperideine由CH在C-3取代的2 OAC组被报告。