N-(2-methylallyl)picolinamide

• 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-(2-methylallyl)picolinamide
• 英文别名: N-(2-methylprop-2-enyl)pyridine-2-carboxamide
• 化学式: C₁₀H₁₂N₂O
• 分子量: 176.218
• InChiKey: HKVGFRKMNCIZJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 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：

  3,4-二氯碘苯 、 N-(2-methylallyl)picolinamide 在 silver(I) acetate 、 palladium diacetate 作用下， 以 甲苯 为溶剂， 反应 36.0h， 以45%的产率得到(Z)-N-(2-(3,4-dichlorobenzyl)-3-(3,4-dichlorophenyl)allyl)picolinamide
  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
• 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-(2-methylallyl)picolinamide
  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

• Palladium(II)-Catalyzed Stereospecific Alkenyl C–H Bond Alkylation of Allylamines with Alkyl Iodides
  作者：Yun-Cheng Luo、Chao Yang、Sheng-Qi Qiu、Qiu-Ju Liang、Yun-He Xu、Teck-Peng Loh

  DOI：10.1021/acscatal.8b04415

  日期：2019.5.3

  A palladium-catalyzed stereospecific alkylation of allylamines with primary and secondary alkyl iodides is described. Isoquinoline-1-carboxamide (IQA) acts as directing group to generate multisubstituted olefin products in cis configuration in moderate to good yields. Mechanistic studies suggest that alkenyl C–H bond activation is the rate-determining step.

  描述了钯催化的烯丙基胺与伯和仲烷基碘的立体有择烷基化。异喹啉-1-羧酰胺（IQA）充当指导基团，以中等至良好的收率生成顺式构型的多取代烯烃产物。机理研究表明，烯基CH键的活化是决定速率的步骤。
• [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
• FUSED HETEROCYCLIC COMPOUNDS AS ION CHANNEL MODULATORS
  申请人：Gilead Sciences, Inc.

  公开号：EP3275870A1

  公开（公告）日：2018-01-31

  The present disclosure relates to compounds that are sodium channel inhibitors and to their use in the treatment of various disease states, including cardiovascular diseases and diabetes. In particular embodiments, the structure of the compounds is given by Formula I: wherein Q, R1, X1, X2, Y and R2 are as described herein, to methods for the preparation and use of the compounds and to pharmaceutical compositions containing the same.

  本公开涉及作为钠通道抑制剂的化合物及其在治疗包括心血管疾病和糖尿病在内的各种疾病状态中的用途。在特定的实施方案中，化合物的结构如式 I 所示： 其中Q、R1、X1、X2、Y和R2如本文所述，涉及化合物的制备和使用方法以及含有这些化合物的药物组合物。