benzoyl(pyridin-1-ium-1-yl)amide | 23031-08-5

• 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: benzoyl(pyridin-1-ium-1-yl)amide
• 英文别名: N-benzoyliminopyridinium ylide；1-(benzoylimino)pyridinium ylide；N-Benzoylimino-pyridinium-betain；(Z)-N-pyridin-1-ium-1-ylbenzenecarboximidate
• CAS: 23031-08-5
• 化学式: C₁₂H₁₀N₂O
• 分子量: 198.224
• InChiKey: JIXGJQGQVBZALF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  39.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  benzoyl(pyridin-1-ium-1-yl)amide 在 palladium bromide 、 三(4-甲氧苯基)膦 、 silver benzoate 、 potassium carbonate 、 copper(ll) bromide 作用下， 以 1,4-二氧六环 为溶剂， 反应 32.08h， 生成 2-phenylpyrazolo[1,5-a]pyridine
  参考文献：
  名称：

  Synthesis of 2- and 2,3-Substituted Pyrazolo[1,5-a]pyridines: Scope and Mechanistic Considerations of a Domino Direct Alkynylation and Cyclization of N-Iminopyridinium Ylides Using Alkenyl Bromides, Alkenyl Iodides, and Alkynes

  摘要：

  Direct functionalization and tandem processes have both received considerable recent interest due to their cost and time efficiency. Herein we report the synthesis of difficult to obtain 2-substituted pyrazolo[1,5-a]pyridines through a tandem palladium-catalyzed/silver-mediated elimination/direct functionalization/cyclization reaction involving N-benzoyliminopyridinium ylides. As such, these biologically important molecules are prepared in an efficient, high-yielding manner, only requiring a two-step sequence from pyridine. Aryl-substituted alkenyl bromides and iodides are effective ylide coupling partners. Mechanistic studies led to the use of terminal alkynes, which extended the scope of the reaction to include alkyl substitution on the unsaturated reactive site. The optimization, scope, and mechanistic considerations of the process are discussed.

  DOI：

  10.1021/jo201303x
• 作为产物：
  描述：

  吡啶 在 2,4-二硝基苯基羟胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 29.08h， 生成 benzoyl(pyridin-1-ium-1-yl)amide
  参考文献：
  名称：

  Synthesis of 2- and 2,3-Substituted Pyrazolo[1,5-a]pyridines: Scope and Mechanistic Considerations of a Domino Direct Alkynylation and Cyclization of N-Iminopyridinium Ylides Using Alkenyl Bromides, Alkenyl Iodides, and Alkynes

  摘要：

  Direct functionalization and tandem processes have both received considerable recent interest due to their cost and time efficiency. Herein we report the synthesis of difficult to obtain 2-substituted pyrazolo[1,5-a]pyridines through a tandem palladium-catalyzed/silver-mediated elimination/direct functionalization/cyclization reaction involving N-benzoyliminopyridinium ylides. As such, these biologically important molecules are prepared in an efficient, high-yielding manner, only requiring a two-step sequence from pyridine. Aryl-substituted alkenyl bromides and iodides are effective ylide coupling partners. Mechanistic studies led to the use of terminal alkynes, which extended the scope of the reaction to include alkyl substitution on the unsaturated reactive site. The optimization, scope, and mechanistic considerations of the process are discussed.

  DOI：

  10.1021/jo201303x

文献信息

• Palladium-Catalyzed Direct C−H Arylation of <i>N</i>-Iminopyridinium Ylides:  Application to the Synthesis of (±)-Anabasine
  作者：Alexandre Larivée、James J. Mousseau、André B. Charette

  DOI：10.1021/ja710073n

  日期：2008.1.1

  Palladium-catalyzed direct C-H arylation of N-iminopyridinium ylides provides a powerful and versatile method for the synthesis of functionalized piperidines in good yields. Chemoselective functionalization of the pyridinium ring in the presence of a pyridine substituent is possible as exemplified by the expedient synthesis of anabasine in 61% overall yield over three steps.

  N-亚氨基吡啶鎓叶立德的钯催化直接 CH 芳基化为以良好的收率合成功能化哌啶提供了一种强大而通用的方法。在吡啶取代基的存在下，吡啶鎓环的化学选择性官能化是可能的，例如通过三个步骤以 61% 的总产率合成 anabasine。
• Copper-Catalyzed Direct Ortho-Alkylation of <i>N</i>-Iminopyridinium Ylides with <i>N</i>-Tosylhydrazones
  作者：Qing Xiao、Lin Ling、Fei Ye、Renchang Tan、Leiming Tian、Yan Zhang、Yuxue Li、Jianbo Wang

  DOI：10.1021/jo4002883

  日期：2013.4.19

  Copper-catalyzed cross-coupling of N-tosylhydrazones with N-iminopyridinium ylides leads to the direct C–H alkylation. This direct C–H bond alkylation transformation uses inexpensive CuI as the catalyst without any ligand. The reaction is operationally simple and conducted under mild conditions, giving the corresponding alkylated pyridines in moderate to good yields. DFT calculation provides insights

  铜催化的N-甲苯磺酰hydr与N-亚氨基吡啶鎓的烷基化物的交叉偶联导致直接的CH烷基化。这种直接的C–H键烷基化转化反应使用廉价的CuI作为催化剂，没有任何配体。该反应操作简单并且在温和的条件下进行，以中等至良好的产率得到相应的烷基化吡啶。DFT计算提供了对反应机理的见解，表明反应是通过Cu卡宾迁移插入过程进行的。
• Visible-Light-Enabled <i>Ortho</i>-Selective Aminopyridylation of Alkenes with <i>N</i>-Aminopyridinium Ylides
  作者：Yonghoon Moon、Wooseok Lee、Sungwoo Hong

  DOI：10.1021/jacs.0c05025

  日期：2020.7.15

  By utilizing an underexplored reactivity mode of N-aminopyridinium ylides, we developed the visible-light-induced ortho-selective aminopyridylation of alkenes via radical-mediated 1,3-dipolar cycloaddition. The photocatalyzed single-electron oxidation of N-aminopyridinium ylides generates the corresponding radical cations that enable previously inaccessible 1,3-cycloaddition with a broader range of

  通过利用 N-氨基吡啶鎓叶立德的未充分探索的反应模式，我们通过自由基介导的 1,3-偶极环加成开发了可见光诱导的烯烃邻位选择性氨基吡啶化。N-氨基吡啶鎓叶立德的光催化单电子氧化产生相应的自由基阳离子，使以前无法实现的1,3-环加成与更广泛的烯烃底物成为可能。所得的环加成加合物迅速进行随后的 NN 键均裂，赋予显着的热力学驱动力以产生各种 β-氨基乙基吡啶。值得注意的是，在无金属和温和条件下，氨基和吡啶基可以通过模块化控制邻位选择性和 1,2- 顺式非对映选择性安装到活化和未活化的烯烃中。
• Micellar Catalysis: Visible‐Light Mediated Imidazo[1,2‐ <i>a</i> ]pyridine C—H Amination with <i>N</i> ‐Aminopyridinium Salt Accelerated by Surfactant in Water
  作者：Zhonglie Yang、Kun Cao、Xiaoyan Peng、Li Lin、Danchen Fan、Jun‐Long Li、Jingxia Wang、Xiaobin Zhang、Hezhong Jiang、Jiahong Li

  DOI：10.1002/cjoc.202100489

  日期：2021.12

  A light-promoted metal-free protocol for the amination of imidazo[1,2-a]pyridines with N-aminopyridinium salt by the assistance of surfactants in water was reported, charactering mild and environmentally benign conditions, as well as great functional group tolerance. Micelles with negatively charged polar surface and hydrophobic core formed from sodium dodecyl sulfate serve as an ideal medium for visible-light

  报道了在水中表面活性剂的辅助下咪唑并[1,2- a ]吡啶与N-氨基吡啶鎓盐胺化的光促进无金属方案，具有温和和环境友好的条件，以及良好的官能团耐受性. 具有带负电荷的极性表面和由十二烷基硫酸钠形成的疏水核的胶束是可见光介导的阳离子吡啶盐和咪唑并[1,2- a ]吡啶在水相中发生自由基反应的理想介质。带正电荷的N-氨基吡啶鎓与带负电荷的胶束表面之间的静电相互作用在该方法中具有重要意义。
• Aryne [3 + 2] cycloaddition with N-sulfonylpyridinium imides and in situ generated N-sulfonylisoquinolinium imides: a potential route to pyrido[1,2-b]indazoles and indazolo[3,2-a]isoquinolines
  作者：Jingjing Zhao、Pan Li、Chunrui Wu、Hongli Chen、Wenying Ai、Renhong Sun、Hailong Ren、Richard C. Larock、Feng Shi

  DOI：10.1039/c2ob06611d

  日期：——

  The aryne [3 + 2] cycloaddition process with pyridinium imides breaks the aromaticity of the pyridine ring. By equipping the imide nitrogen with a sulfonyl group, the intermediate readily eliminates a sulfinate anion to restore the aromaticity, leading to the formation of pyrido[1,2-b]indazoles. The scope and limitation of this reaction are discussed. As an extension of this chemistry, N-tosylisoquinolinium

  与吡啶鎓酰亚胺的芳烃[3 + 2]环加成过程破坏了吡啶环的芳香性。通过在酰亚胺氮上加成磺酰基，该中间体容易消除亚磺酸根阴离子以恢复芳香性，从而导致吡啶并[1,2- b ]吲唑的形成。讨论了该反应的范围和局限性。作为该化学反应的扩展，通过AgOTf催化的6-endo-dig亲电环化反应从N '-（2-炔基亚苄基）-甲苯磺酰肼原位生成的N-甲苯磺酰异喹啉鎓亚胺易于进行芳烃[3 + 2]环加成反应而制得吲哚唑[3,2- a同一锅中的]-异喹啉，为这些潜在的抗癌药提供了高效途径。