N-allylpicolinamide | 861018-87-3

• 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: N-allylpicolinamide
• 英文别名: N-(prop-2-en-1-yl)pyridine-2-carboxamide；N-prop-2-enylpyridine-2-carboxamide
• CAS: 861018-87-3
• 化学式: C₉H₁₀N₂O
• mdl: MFCD20355236
• 分子量: 162.191
• InChiKey: SLWIPNGFDAIIJA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.111
• 拓扑面积：
  42
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-allylpicolinamide 在 碘代三甲硅烷 、 碘苯二乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以85%的产率得到5-(iodomethyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole
  参考文献：
  名称：

  Modular Preparation of 5-Halomethyl-2-oxazolines via PhI(OAc)₂-Promoted Intramolecular Halooxygenation of N-Allylcarboxamides

  摘要：

  A new method for the construction of oxazoline moiety was detailed. Using (diacetoxyiodo)benzene (PIDA) as the reaction promoter and halotrimethylsilane as the halogen source, intramolecular halooxygenation and halothionation of N-allylcarboxamides/N-allylcarbothioamides proceeded readily, leading : to the corresponding 5-halomethyloxazolines/5-halomethylthiazolines in good to excellent isolated yields. The 5-halomethyl products could be converted to different derivatives via conventional nucleophilic substitution methods. The reactions were carried out using easily available starting materials, and did not need harsh reaction conditions. All these features made this reaction a viable method for the construction of different oxazoline and thiazoline structures.

  DOI：

  10.1021/acs.joc.5b01832
• 作为产物：
  描述：

  2-吡啶甲酸 在 4-二甲氨基吡啶 、 草酰氯 、 三乙胺 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 N-allylpicolinamide
  参考文献：
  名称：

  Pd(II)-Catalyzed, Picolinamide-Assisted, Z-Selective γ-Arylation of Allylamines To Construct Z-Cinnamylamines

  摘要：

  Investigations of Pd(II)-catalyzed, picolinamide-assisted, gamma-C(sp(2))-H activation and Z-selective arylation of allylamines are reported. The reactions of N-allylpicolinamides with various aryl iodides in the presence of the catalyst Pd(OAc)(2) and additive AgOAc have led to the selective gamma-arylation of allylamines to construct various cinnamylamines with moderate to good yields and good to high E/Z ratios. To obtain good E/Z ratios, the Pd(II)-catalyzed arylation reaction of N-allylpicolinamides was probed using different additives, directing groups, and reaction conditions. The Pd(II)-catalyzed arylation of an allylamine containing both gamma-C(sp(2))-(H) and gamma-C(sp(3)) H bonds afforded moderate yields of the gamma-C(sp(2)) H and gamma-C(sp3) H bisarylated cinnamylamines. Although Heck-type gamma-arylations of allylamines have generally afforded the E-cinnamylamines, the bidentate directing group picolinamide-directed arylations of allylamines were found to be Z-selective. A plausible mechanism was proposed for the observed regioselectivity and Z-selective arylation of N-allylpicolinamides. Additionally, the Pd(II)-catalyzed arylation of an N-allyl-5-methylisoxazole-3-carboxamide afforded the E-cinnarnylamines plausibly via a ligand-free Heck-type reaction mechanism.

  DOI：

  10.1021/acs.joc.7b00535

文献信息

• [Cp*Rh^III ] in an Ionic Liquid as a Highly Efficient and Recyclable Catalytic Medium for Regio- and Diastereoselective Csp³ -H Carbenoid Insertion
  作者：Jianglian Li、Lin Zhou、Yaoling Wang、Qiang Ma、Yuan Lei、Ruizhi Lai、Yi Luo、Li Hai、Yong Wu

  DOI：10.1002/ejoc.201901279

  日期：2019.12.8

  A bidentate‐assisted Csp3–H bond insertion using Cp*RhIII/IL as a highly efficient and recyclable catalytic medium is reported. The application of ionic liquid not only lowered the temperature, but also enhanced the diastereoselectivity of this reaction. This work significantly expanded the scope of ionic liquids in Csp3–H functionalizations

  据报道，使用Cp * Rh III / IL作为高效且可回收的催化介质，可进行双齿辅助的Csp 3 -H键插入。离子液体的应用不仅降低了温度，而且提高了该反应的非对映选择性。这项工作大大扩展了Csp 3 -H官能化中离子液体的范围
• Highly chemoselective, sterically sensitive NHC-catalysed amine acylation with pyridil
  作者：Amy C. Maguire、Vikas Kumar、Stephen J. Connon

  DOI：10.1039/c9cc06937b

  日期：——

  A new strategy for the protection of amines has been developed involving reaction with pyridil under the influence of N-heterocyclic carbene catalysis. The methodology is capable of distinguishing between two amines characterised by small differences in steric bulk and the resulting pyridoyl amides can be cleaved without requiring either strongly acidic or basic hydrolysis.

  已经开发了一种保护胺的新策略，该策略涉及在N-杂环卡宾催化作用下与吡啶酮反应。该方法能够区分以空间体积小的差异为特征的两种胺，并且可以裂解得到的吡啶基酰胺，而无需强酸性或碱性水解。
• Rh(<scp>iii</scp>)-catalyzed regioselective intermolecular <i>N</i>-methylene Csp³–H bond carbenoid insertion
  作者：Haisheng Xie、Zongren Ye、Zhuofeng Ke、Jianyong Lan、Huanfeng Jiang、Wei Zeng

  DOI：10.1039/c7sc03802j

  日期：——

  A Rh(III)-catalyzed regioselective intermolecular carbenoid insertion into the N-methylene Csp3–H bond of acyclic aliphatic amides has been achieved, taking advantage of bidentate–chelation assistance. This methodology has been successfully applied to a broad range of linear and branched-chain N-alkylamides, thus providing a practical method for the assembly of diverse beta-amino esters. Mechanism

  利用二齿螯合的辅助作用，实现了Rh（III）催化的区域选择性分子间类胡萝卜素插入无环脂族酰胺的N-亚甲基Csp 3 -H键中。该方法已经成功地应用于各种线性和支链的N-烷基酰胺，因此为组装各种β-氨基酯提供了一种实用的方法。机理研究和密度泛函理论（DFT）计算表明，这种N-亚甲基Csp 3 -H键类胡萝卜素插入过程涉及通过外球途径的单线Fischer型卡宾插入。
• Copper Catalyzed C–N Cross-Coupling Reaction of Aryl Boronic Acids at Room Temperature through Chelation Assistance
  作者：Harekrishna Sahoo、Sayan Mukherjee、Gowri Sankar Grandhi、Jayaraman Selvakumar、Mahiuddin Baidya

  DOI：10.1021/acs.joc.7b00002

  日期：2017.3.3

  A copper-catalyzed selective C–N cross-coupling has been developed based on chelation-assisted amidation of readily available aryl boronic acids at room-temperature under open-flask conditions. The reaction is scalable and tolerates a wide spectrum of functional groups delivering fully substituted unsymmetrical amides in high yields (up to 96%). The C–N cross coupling also established with aryl silanes

  铜催化的选择性C–N交叉偶联已基于在易开罐条件下于室温下容易获得的芳基硼酸的螯合辅助酰胺化作用而开发。该反应具有可扩展性，并能耐受各种官能团，从而以高收率（高达96％）提供完全取代的不对称酰胺。C–N交叉偶联也可与芳基硅烷建立，从而扩展了该策略偶联伙伴的范围。
• The Triphenyl Phosphite-Chlorine Reagent in the Synthesis of Pyrroles from<i>N</i>-Allylamides
  作者：Fabio Prati、Alberto Spaggiari、Daniele Vaccari、Paolo Davoli

  DOI：10.1055/s-2006-926365

  日期：——

  A novel application of (PhO) 3 P-Cl 2 chemistry to the synthesis of 2-substituted and 2,3-disubstituted pyrroles from N-allylamides is illustrated. A mild procedure is used to generate the imino chloride intermediates, which are subsequently cyclized to pyrroles. The products are smoothly obtained in moderate to good overall yields.

  说明了 (PhO) 3 P-Cl 2 化学在从 N-烯丙基酰胺合成 2-取代和 2,3-二取代吡咯的新应用。使用温和的程序生成亚氨基氯化物中间体，随后将其环化为吡咯。产品以中等至良好的总产率顺利获得。