1-benzyl-2-methyl-6-oxo-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid ethyl ester | 23213-78-7

• 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: 1-benzyl-2-methyl-6-oxo-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid ethyl ester
• 英文别名: ethyl 1-benzyl-6-methyl-2-oxo-3,4-dihydropyridine-5-carboxylate
• CAS: 23213-78-7
• 化学式: C₁₆H₁₉NO₃
• 分子量: 273.332
• InChiKey: VEAQWKUTPSSGEX-UHFFFAOYSA-N

物化性质

• 沸点：
  434.7±45.0 °C(Predicted)
• 密度：
  1.159±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-benzyl-2-methyl-6-oxo-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid ethyl ester 在 palladium on activated charcoal 氢气 、 sodium carbonate 作用下， 以 乙醇 为溶剂， 以91%的产率得到(2R,3R)-1-Benzyl-2-methyl-6-oxo-piperidine-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  “通过区域选择性控制的氮杂-环化制备的构象受限的β-氨基酸等排体。”

  摘要：

  多种吸电子取代基用于增强烯胺与丙烯酰氯的氮杂-环氧化，以指导烯烃形成的区域选择性，并促进不饱和环化产物的氢化。所得的δ-内酰胺产物是β-氨基酸类似物，其结构特征与已建立的肽等排物相似。

  DOI：

  10.1016/s0040-4039(00)61389-8
• 作为产物：
  描述：

  丙烯酸酐 、 ethyl 3-(benzylamino)crotonate 以 四氢呋喃 为溶剂， 生成 1-benzyl-2-methyl-6-oxo-1,4,5,6-tetrahydro-pyridine-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  Heterocycle formation through aza-annulation: A stereochemically controlled route to (±)-lupinine.

  摘要：

  The aza-annulation of an acyclic beta-enaminoester with acryloyl chloride was found to be a very efficient method for nitrogen heterocycle formation. Stereospecific hydrogenation of the unsaturated dihydropyridone generated from aza-annulation gave a single disubstituted lactam product. The cis stereochemical relationship of the substituents was confirmed by transformation of the lactam to (+/-)-lupinine.

  DOI：

  10.1016/s0040-4039(00)60550-6

文献信息

• “Conformationally restricted β-amino acid isosteres prepared through regioselectively controlled aza-annulation.”
  作者：K. Paulvannan、John R. Stille

  DOI：10.1016/s0040-4039(00)61389-8

  日期：1993.12

  A variety of electron withdrawing substituents were used to enhance the aza-annulation of enamines with acryloyl chloride, to direct the regioselectivity of alkene formation, and to facilitate hydrogenation of the unsaturated annulation product. The resulting δ-lactam products were β-amino acid analogs with structural features similar to those of established peptide isosteres.

  多种吸电子取代基用于增强烯胺与丙烯酰氯的氮杂-环氧化，以指导烯烃形成的区域选择性，并促进不饱和环化产物的氢化。所得的δ-内酰胺产物是β-氨基酸类似物，其结构特征与已建立的肽等排物相似。
• Heterocycle formation through aza-annulation: A stereochemically controlled route to (±)-lupinine.
  作者：K. Paulvannan、Jacob B. Schwarz、John R. Stille

  DOI：10.1016/s0040-4039(00)60550-6

  日期：1993.1

  The aza-annulation of an acyclic beta-enaminoester with acryloyl chloride was found to be a very efficient method for nitrogen heterocycle formation. Stereospecific hydrogenation of the unsaturated dihydropyridone generated from aza-annulation gave a single disubstituted lactam product. The cis stereochemical relationship of the substituents was confirmed by transformation of the lactam to (+/-)-lupinine.
• Heterocycle Formation through Aza-Annulation: Stereochemically Controlled Syntheses of (.+-.)-5-Epitashiromine and (.+-.)-Tashiromine
  作者：K. Paulvannan、John R. Stille

  DOI：10.1021/jo00086a009

  日期：1994.4

  N-alkylenamines, stabilized through conjugation with an electron-withdrawing group, undergo aza-annulation with acryloyl chloride to provide a convergent route for the construction of six-membered nitrogen heterocycles. In addition to enhancing the C-alkylation process of annulation relative to the competing N-acylation process, the electron withdrawing substituent controlled the regioselectivity of alkene formation in both the intermediate enamine and in the unsaturated lactam product. A variety of functional groups, which include -COMe, -COPh, -CO(2)R, -CONHPh, -CN, -P(O)(OEt)(2), and -SO(2)Ph, were used to determine the effect of the electron-withdrawing substituents upon both the annulation reaction with acryloyl chloride and the subsequent hydrogenation process. When the enamide annulation product was stabilized through conjugation with ester or amide substituents, catalytic hydrogenation of the ate-annulation product resulted in the formation of vicinal stereocenters with high cis selectivity. The utility of this methodology was demonstrated by application of the condensation/aza-annulation/hydrogenation sequence as the key for construction and stereochemical control of the indolizidine ring system of (+/-)-tashiromine.