1-(6-methyl-1-oxido-2-pyridinyl)ethanone | 1563017-55-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(6-methyl-1-oxido-2-pyridinyl)ethanone
• CAS: 1563017-55-9
• 化学式: C₈H₉NO₂
• 分子量: 151.165
• InChiKey: GQZCESPGKFBOBJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.83
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  44.01
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(6-methyl-1-oxido-2-pyridinyl)ethanone 、 2,2-difluoro-1-phenyl-1-trimethylsiloxyethene 在 copper(II) bis(tetrafluoroborate) 作用下， 以 四氢呋喃 为溶剂， 生成 2-(3,3-difluoro-2-hydroxy-4-oxo-4-phenylbutan-2-yl)-6-methylpyridine 1-oxide
  参考文献：
  名称：

  Cu-BOX 催化的对映选择性 Mukaiyama-aldol 反应与二氟化甲硅烷基烯醇醚和酰基吡啶 N-氧化物

  摘要：

  Cu( II )/BOX 络合物催化二氟化甲硅烷基烯醇醚对映选择性加成酰基吡啶N-氧化物。该反应提供了在药物化学中具有重要意义的二氟化手性叔醇。这些化合物以中等到极好的产率和高对映体选择性获得。反应的立体化学结果已通过 DFT 计算得到解释。

  DOI：

  10.1039/d2ob01763f
• 作为产物：
  描述：

  2-乙酰基-6-甲基吡啶 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以94%的产率得到1-(6-methyl-1-oxido-2-pyridinyl)ethanone
  参考文献：
  名称：

  Enantioselective Addition of Nitromethane to 2-Acylpyridine N-Oxides. Expanding the Generation of Quaternary Stereocenters with the Henry Reaction

  摘要：

  The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or alpha-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.

  DOI：

  10.1021/ol500082d

文献信息

• Catalytic enantioselective Henry reaction of α-keto esters, 2-acylpyridines and 2-acylpyridine <i>N</i>-oxides
  作者：Feilong He、Guanghui Chen、Junxia Yang、Guojuan Liang、Ping Deng、Yan Xiong、Hui Zhou

  DOI：10.1039/c8ra00552d

  日期：——

  catalytic asymmetric Henry reaction of α-keto esters, 2-acylpyridines and 2-acylpyridine N-oxides. The corresponding β-nitro-α-hydroxy esters were obtained in good to excellent yields (up to 99%) with a high enantiomeric excess (ee) (up to 94%) with a catalyst loading of 1–2 mol%. The desired products of 2-acylpyridines and 2-acylpyridine N-oxides, which were simple methyl ketones, were obtained in medium

  已经开发了一种预先制备的 Ni-PyBisulidine 配合物，用于 α-酮酯、2-酰基吡啶和 2-酰基吡啶 N-氧化物的催化不对称亨利反应。相应的 β-硝基-α-羟基酯在催化剂负载量为 1-2 mol% 的情况下以良好至优异的产率（高达 99%）和高对映体过量（ee）（高达 94%）获得。2-酰基吡啶和 2-酰基吡啶N-氧化物的所需产物是简单的甲基酮，通过使用 2 mol% 以中等至优异的产率（高达 94%）获得中等至良好的 ee（高达 86%）的催化剂。
• Asymmetric Henry Reaction of 2-Acylpyridine N-Oxides Catalyzed by a Ni-Aminophenol Sulfonamide Complex: An Unexpected Mononuclear Catalyst
  作者：Mouxiong Liu、Dongdong Gui、Ping Deng、Hui Zhou

  DOI：10.3390/molecules24081471

  日期：——

  The asymmetric Henry reaction of 2-acylpyridine N-oxide remains a challenge as N-oxides generally act as competitive catalyst inhibitors or displace activating ligands. A novel variable yield (up to 99%) asymmetric Henry reaction of 2-acypyridine N-oxides catalyzed by a Ni-aminophenol sulfonamide complex with good to excellent enantioselectivity (up to 99%) has been developed. Mechanistic studies suggest that the unique properties of the electron-pairs of N-oxides for complexation with Ni makes the unexpected mononuclear complex, rather than the previously reported dinuclear complex, the active species.

  2-酰基吡啶N-氧的不对称Henry反应仍然是一个挑战，因为N-氧通常作为竞争性催化剂抑制剂或取代活化配体。一种新的变化产率（高达99%）的2-酰基吡啶N-氧不对称Henry反应，由Ni-氨基酚磺胺酰胺复合物催化，具有良好至优异的对映选择性（高达99%）。机理研究表明，N-氧的电子对的独特性质与Ni形成络合物，使得意外的单核复合物成为活性物种，而不是先前报道的二核复合物。
• Enantioselective Addition of Nitromethane to 2-Acylpyridine <i>N</i>-Oxides. Expanding the Generation of Quaternary Stereocenters with the Henry Reaction
  作者：Melireth Holmquist、Gonzalo Blay、M. Carmen Muñoz、José R. Pedro

  DOI：10.1021/ol500082d

  日期：2014.2.21

  The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or alpha-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.
• A Cu-BOX catalysed enantioselective Mukaiyama-aldol reaction with difluorinated silyl enol ethers and acylpyridine <i>N</i>-oxides
  作者：Amparo Sanz-Marco、Daniel Esperilla、Marc Montesinos-Magraner、Carlos Vila、M. Carmen Muñoz、José R. Pedro、Gonzalo Blay

  DOI：10.1039/d2ob01763f

  日期：——

  A Cu(II)/BOX complex catalyses the enantioselective addition of difluorinated silyl enol ethers to acylpyridine N-oxides. The reaction provides difluorinated chiral tertiary alcohols of great interest in medicinal chemistry. These compounds are obtained in moderate to excellent yields and with high enantioselectivities. The stereochemical outcome of the reaction has been explained by DFT calculations

  Cu( II )/BOX 络合物催化二氟化甲硅烷基烯醇醚对映选择性加成酰基吡啶N-氧化物。该反应提供了在药物化学中具有重要意义的二氟化手性叔醇。这些化合物以中等到极好的产率和高对映体选择性获得。反应的立体化学结果已通过 DFT 计算得到解释。