p-cyanopyridine benzoylnitrene ylide | 605670-88-0

• 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: p-cyanopyridine benzoylnitrene ylide
• 英文别名: 4-cyano-N-benzoyliminopyridinium ylide；N-(4-cyanopyridin-1-ium-1-yl)benzenecarboximidate
• CAS: 605670-88-0
• 化学式: C₁₃H₉N₃O
• 分子量: 223.234
• InChiKey: XAYBTMRGWPXAOT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  17
• 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：
  63.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  p-cyanopyridine benzoylnitrene ylide 以 乙腈 为溶剂， 生成 benzoyl nitrene
  参考文献：
  名称：

  乙酰基和甲氧基羰基氮烯的计算方法比较和苯甲酰亚硝基苯胺的激光闪光光解研究

  摘要：

  进行密度泛函理论（DFT），CCSD（T）和CBS-QB3计算以了解乙酰基丁二烯（CH 3 C（O）N）和甲氧基羰基丁二烯（CH 3 OC（O）N）和相关化合物。单独的CBS-QB3理论正确地预测出乙炔基具有单重态基态。我们同意先前的研究，认为单线态乙炔基丁烯中存在大量的N-O相互作用，而在甲氧基羰基丁二烯中发现了相应的但较弱的相互作用。甲氧基羰基氮烯具有三重态基态，这是因为氧原子比相应的单重态更稳定羰基腈的三重态。氧原子还稳定了库尔修斯重排的过渡态，并加速了甲氧基羰基氮杂烯相对于乙酰基氮杂烯的异构化。乙酰叠氮化物经计算通过甲基的协同迁移以及氮的挤出而分解；该协同过程的活化自由能仅为27 kcal / mol，乙酰叠氮化物热解时不会产生游离的氮。另一方面，甲氧羰基叠氮化物确实优选通过游离的氮逐步进行Curtius重排。计算出乙炔和甲氧羰基丁烯与丙烷，乙烯和甲醇的双分子反应，发现其焓垒接近于

  DOI：

  10.1021/jo048433y
• 作为产物：
  描述：

  4-氰基吡啶 在 2,4-二硝基苯基羟胺 、 sodium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 21.08h， 生成 p-cyanopyridine benzoylnitrene ylide
  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

• Benzoyl Peroxide Promoted Radical<i>ortho</i>-Alkylation of Nitrogen Heteroaromatics with Simple Alkanes and Alcohols
  作者：Lei Fang、Liangshun Chen、Jianjun Yu、Limin Wang

  DOI：10.1002/ejoc.201403479

  日期：2015.3

  A catalytic amount of benzoyl peroxide (BPO)-initiated cross-dehydrogenative coupling reaction of N-iminopyridine ylides with simple alkanes and alcohols leads to the corresponding 2-alkylpyridines with high regioselectivity in moderate to good yields without an additional reduction step to remove the activated group.

  催化量的过氧化苯甲酰 (BPO) 引发的 N-亚氨基吡啶叶立德与简单烷烃和醇的交叉脱氢偶联反应导致相应的 2-烷基吡啶具有高区域选择性，产率中等至良好，无需额外的还原步​​骤来去除活化团体。
• Highly Efficient Synthesis of <i>O</i>-(2,4-Dinitrophenyl)hydroxylamine. Application to the Synthesis of Substituted <i>N</i>-Benzoyliminopyridinium Ylides
  作者：Claude Legault、André B. Charette

  DOI：10.1021/jo034456l

  日期：2003.9.1

  efficient two-step synthesis of O-(2,4-dinitrophenyl)hydroxylamine is described along with a comparison of its aminating efficiency with O-mesitylenesulfonylhydroxylamine (MSH). It was used in an expedient N-amination/benzoylation procedure involving various substituted pyridines, leading to polysubstituted N-benzoyliminopyridinium ylides, and the scope of its amination power was studied.

  描述了一种有效的两步合成O-（2,4-二硝基苯基）羟胺的方法，并比较了其与O-次甲基亚磺酰基羟胺（MSH）的胺化效率。它被用于方便的N-氨基化/苯甲酰化过程，涉及各种取代的吡啶，导致多取代的N-苯并亚氨基吡啶基吡啶化，并研究了其胺化能力的范围。
• 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。
• Photochemical Skeletal Editing of Pyridines to Bicyclic Pyrazolines and Pyrazoles
  作者：Jiajing Luo、Qingyang Zhou、Zhou Xu、K. N. Houk、Ke Zheng

  DOI：10.1021/jacs.4c03713

  日期：2024.8.7

  We present an efficient one-pot photochemical skeletal editing protocol for the transformation of pyridines into diverse bicyclic pyrazolines and pyrazoles under mild conditions. The method requires no metals, photocatalysts, or additives and allows for the selective removal of specific carbon atoms from pyridines, allowing for unprecedented versatility. Our approach offers a convenient and efficient

  我们提出了一种有效的一锅光化学骨架编辑方案，用于在温和条件下将吡啶转化为多种双环吡唑啉和吡唑。该方法不需要金属、光催化剂或添加剂，并且可以选择性地从吡啶中去除特定的碳原子，从而实现了前所未有的多功能性。我们的方法通过替换核心吡啶骨架，为复杂药物分子的后期修饰提供了一种方便有效的方法。此外，我们已经成功地在停流和流动化学系统中扩展了该过程，展示了其对复杂转化的适用性，例如狄尔斯-阿尔德反应、氢化、[3 + 2]环加成和赫克反应。通过控制实验和 DFT 计算，我们深入了解了这种骨架编辑协议的机制基础。