2-(p-tolyl)pyrazolo[1,5-a]pyridine | 1206884-50-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-(p-tolyl)pyrazolo[1,5-a]pyridine
• 英文别名: 2-(4-Methylphenyl)pyrazolo[1,5-a]pyridine；2-(4-methylphenyl)pyrazolo[1,5-a]pyridine
• CAS: 1206884-50-5
• 化学式: C₁₄H₁₂N₂
• 分子量: 208.263
• InChiKey: ROHOLCKGXHJSOW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  17.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  碳酸亚乙烯酯 、 2-(p-tolyl)pyrazolo[1,5-a]pyridine 在 tris(acetonitrile)(η5-pentamethylcyclopentadienyl)rhodium(III) hexafluoroantimonate 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 24.0h， 以90%的产率得到3-methylbenzo[g]pyrido[1,2-b]indazole
  参考文献：
  名称：

  咪唑吡啶和吲唑通过铑催化的乙烯基转移的氧化CH / CH环化反应。

  摘要：

  过渡金属催化的CH活化，然后与炔烃进行氧化环化反应，已成为组装各种聚芳烃支架的有效合成工具。尽管在该领域取得了很大进展，但是实现非取代的亚乙烯基稠合化合物的合成仍然是一个重大挑战。在这一贡献中，我们报告了采用碳酸亚乙烯酯作为“亚乙烯基转移”剂的Rh催化的CH / CH亚乙烯基环化反应。该协议实现了咪唑和吡唑融合的芳族化合物的直接环π延伸。

  DOI：

  10.1021/acs.orglett.0c00975
• 作为产物：
  描述：

  N-iminopyridinium ylide 在 palladium bromide 、 三(4-甲氧苯基)膦 、 silver benzoate 、 sodium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 水 为溶剂， 反应 21.08h， 生成 2-(p-tolyl)pyrazolo[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

文献信息

• From N-benzoylpyridinium imides to pyrazolo[1,5-a]pyridines: a mechanistic discussion on a stoichiometric Cu protocol
  作者：Lin Ling、Jingqing Chen、Jiahui Song、Yuhai Zhang、Xinqian Li、Lijuan Song、Feng Shi、Yuxue Li、Chunrui Wu

  DOI：10.1039/c3ob40448j

  日期：——

  A Cu-mediated preparation of 2-substitiuted pyrazolo[1,5-a]pyridines from N-benzoylpyridinium imides and terminal alkynes is described using stoichiometric Cu(OAc)2 as both the mediator and the oxidant. Extensive DFT calculations suggest a Cu(III) intermediate via disproportionation of Cu(II).

  描述了使用化学计量的Cu（OAc）2作为介体和氧化剂，由N-苯甲酰基吡啶鎓酰亚胺和末端炔烃组成的Cu介导的2取代吡唑并[1,5- a ]吡啶的制备方法。广泛的DFT计算表明，通过Cu（II）歧化可以生成Cu（III）中间体。
• Copper-catalyzed direct oxidative annulation of N-iminopyridinium ylides with terminal alkynes using O₂as oxidant
  作者：Shengtao Ding、Yuepeng Yan、Ning Jiao

  DOI：10.1039/c2cc33706a

  日期：——

  The aerobic direct dehydrogenative annulation of N-iminopyridinium ylides with terminal alkynes leading to pyrazolo[1,5-a]pyridine derivatives has been developed.

  已开发了N-亚氨基吡啶鎓的有氧烷与末端炔烃的好氧直接脱氢环化反应，产生吡唑并[1,5-a]吡啶衍生物。
• Synthesis of 2-Substituted Pyrazolo[1,5-<i>a</i>]pyridines through Cascade Direct Alkenylation/Cyclization Reactions
  作者：James J. Mousseau、Angélique Fortier、André B. Charette

  DOI：10.1021/ol902710f

  日期：2010.2.5

  from N-iminopyridinium ylides is described. These medicinally interesting compounds are formed through a cascade process involving a palladium-catalyzed direct alkenylation reaction followed by silver-mediated cyclization. The reaction can be performed with a wide range of electron-poor and electron-rich alkenyl iodides in good yields. This work represents perhaps the most direct route for the preparation

  描述了由N-亚氨基吡啶鎓的叶立德合成2-取代的吡唑并[1，5- a ]吡啶。这些医学上有趣的化合物是通过级联过程形成的，该过程涉及钯催化的直接烯基化反应，然后进行银介导的环化反应。该反应可与多种贫电子和富电子的烯基碘化物以高收率进行。这项工作可能代表了制备这些化合物的最直接途径。
• Base-mediated [3 + 2]-cycloannulation strategy for the synthesis of pyrazolo[1,5-<i>a</i>]pyridine derivatives using (<i>E</i>)-β-iodovinyl sulfones
  作者：Raju Jannapu Reddy、Nunavath Sharadha、Arram Haritha Kumari

  DOI：10.1039/d2ob00499b

  日期：——

  with 1-aminopyridinium iodide is realized to access 2-substituted pyrazolo[1,5-a]pyridines in good to high yields. An essential modification of the dipolar N-tosylpyridinium imide allows the first preparative synthesis of 3-sulfonyl-pyrazolo[1,5-a]pyridines in moderate to high yields. Of note, the metal-free protocol features a broad substrate scope with good functional group tolerance and compatibility

  吡唑并[1,5- a ]吡啶继续在药物化学中占据特殊地位，但3-磺酰基类似物的直接构建仍未探索。在碱性条件下，吡啶鎓-N-胺和相应的偶极胺在使用( E )-β-碘乙烯基砜的[3 + 2]-环加成反应中发挥了重要作用。K 2 CO 3介导的 ( E )-β-碘乙烯基砜与 1-氨基吡啶碘化物的串联环环脱磺酰基化反应以良好至高产率获得 2-取代的吡唑并[1,5- a ]吡啶。偶极N的基本修改-tosylpyridinium imide 首次以中等至高产率制备合成 3-磺酰基-吡唑并[1,5- a ] 吡啶。值得注意的是，无金属协议具有广泛的底物范围，具有良好的官能团耐受性和兼容性。通过克级反应证明了该过程的有效性，并根据具体结果提出了合理的机制。
• Synthesis of 2- and 2,3-Substituted Pyrazolo[1,5-<i>a</i>]pyridines: Scope and Mechanistic Considerations of a Domino Direct Alkynylation and Cyclization of <i>N</i>-Iminopyridinium Ylides Using Alkenyl Bromides, Alkenyl Iodides, and Alkynes
  作者：James J. Mousseau、James A. Bull、Carolyn L. Ladd、Angélique Fortier、Daniela Sustac Roman、André B. Charette

  DOI：10.1021/jo201303x

  日期：2011.10.21

  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.