5-acetyl-1-benzyl-6-methyl-3,4-dihydro-1H-pyridin-2-one | 32402-69-0

• 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: 5-acetyl-1-benzyl-6-methyl-3,4-dihydro-1H-pyridin-2-one
• 英文别名: 5-acetyl-1-benzyl-6-methyl-3,4-dihydro-1H-pyridin-2-one；5-acetyl-1-benzyl-6-methyl-3,4-dihydropyridin-2-one
• CAS: 32402-69-0
• 化学式: C₁₅H₁₇NO₂
• 分子量: 243.305
• InChiKey: GRASVBXDTYYLMH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  5-acetyl-1-benzyl-6-methyl-3,4-dihydro-1H-pyridin-2-one 在 sodium hydroxide 作用下， 反应 12.0h， 生成 (5S,6R)-1-Benzyl-5-hydroxy-6-methyl-piperidin-2-one
  参考文献：
  名称：

  Construction of Hydroxylated Alkaloids (.+-.)-Mannonolactam, (.+-.)-Deoxymannojirimycin, and (.+-.)-Prosopinine through Aza-Annulation

  摘要：

  The aza-annulation of beta enamino carbonyl substrates with acrylate derivatives provides an efficient and convenient route for the regioselective construction of delta-lactams. This two-step ring-forming sequence involved initial generation of the benzyl enamine through either a condensation or conjugate addition reaction with BnNH(2), followed by aza-annulation with acryloyl chloride or acrylic anhydride. Controlled by the rigid framework of the intermediate lactam, introduction of ring substituents was accomplished with high relative stereoselectivity. The carbonyl functionality, which was necessary to direct the regioselectivity of the aza-annulation reaction, was then transformed into a protected hydroxyl substituent through Baeyer-Villiger oxidation. The resultant delta-lactam product was used as a valuable intermediate in the synthesis of three natural products. Subsequent modification of this delta-lactam gave the naturally occurring alpha-mannosidase inhibitors (+/-)-mannonolactam and (+/-)deoxymannojirimycin, while synthesis of the alkaloid (+/-)-prosopinine was accomplished through homologation of the lactam carbonyl.

  DOI：

  10.1021/jo00092a015
• 作为产物：
  描述：

  (Z)-4-(benzylamino)-3-penten-2-one 、 丙烯酰氯 以 四氢呋喃 为溶剂， 生成 5-acetyl-1-benzyl-6-methyl-3,4-dihydro-1H-pyridin-2-one
  参考文献：
  名称：

  Stereoselective synthesis of 5-alkyliden-6-aminotetrahydro-2-pyranones through an unexpected isomerization of the hydroxytetrahydro-2-pyridinones obtained by the selective reduction of acylated enaminones

  摘要：

  A convenient methodology for the stereoselective preparation of 5-alkyliden-6-aminotetrahydro-2-pyranone 4 is reported. The synthesis of 2-pyranone 4 occurs through an unknown isomerization mechanism of the hydroxytetrahydro-2-pyridinone 3, an accessible starling material obtained by mild and selective reduction of the 5-acyltetrahydro-2-pyridinone 2. The isomerization mechanism and the stereoselectivity in the synthesis of 2-pyranone 4 was investigated and rationalized. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(97)10333-7

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: 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.
• Construction of Hydroxylated Alkaloids (.+-.)-Mannonolactam, (.+-.)-Deoxymannojirimycin, and (.+-.)-Prosopinine through Aza-Annulation
  作者：Gregory R. Cook、Lars G. Beholz、John R. Stille

  DOI：10.1021/jo00092a015

  日期：1994.7

  The aza-annulation of beta enamino carbonyl substrates with acrylate derivatives provides an efficient and convenient route for the regioselective construction of delta-lactams. This two-step ring-forming sequence involved initial generation of the benzyl enamine through either a condensation or conjugate addition reaction with BnNH(2), followed by aza-annulation with acryloyl chloride or acrylic anhydride. Controlled by the rigid framework of the intermediate lactam, introduction of ring substituents was accomplished with high relative stereoselectivity. The carbonyl functionality, which was necessary to direct the regioselectivity of the aza-annulation reaction, was then transformed into a protected hydroxyl substituent through Baeyer-Villiger oxidation. The resultant delta-lactam product was used as a valuable intermediate in the synthesis of three natural products. Subsequent modification of this delta-lactam gave the naturally occurring alpha-mannosidase inhibitors (+/-)-mannonolactam and (+/-)deoxymannojirimycin, while synthesis of the alkaloid (+/-)-prosopinine was accomplished through homologation of the lactam carbonyl.
• Stereoselective synthesis of 5-alkyliden-6-aminotetrahydro-2-pyranones through an unexpected isomerization of the hydroxytetrahydro-2-pyridinones obtained by the selective reduction of acylated enaminones
  作者：Cristina Cimarelli、Gianni Palmieri

  DOI：10.1016/s0040-4020(97)10333-7

  日期：1998.1

  A convenient methodology for the stereoselective preparation of 5-alkyliden-6-aminotetrahydro-2-pyranone 4 is reported. The synthesis of 2-pyranone 4 occurs through an unknown isomerization mechanism of the hydroxytetrahydro-2-pyridinone 3, an accessible starling material obtained by mild and selective reduction of the 5-acyltetrahydro-2-pyridinone 2. The isomerization mechanism and the stereoselectivity in the synthesis of 2-pyranone 4 was investigated and rationalized. (C) 1997 Elsevier Science Ltd. All rights reserved.