4-chloro-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: 4-chloro-N-(2-methylallyl)picolinamide
• 英文别名: 4-chloro-N-(2-methylprop-2-enyl)pyridine-2-carboxamide
• 化学式: C₁₀H₁₁ClN₂O
• 分子量: 210.663
• InChiKey: VTGXWFMZCZGUBM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  14
• 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：

  5-溴-2-碘吡啶 、 4-chloro-N-(2-methylallyl)picolinamide 在 silver(I) acetate 、 palladium diacetate 作用下， 以 甲苯 为溶剂， 反应 48.0h， 以40%的产率得到(Z)-N-(3-(5-bromopyridin-2-yl)-2-methylallyl)-4-chloropicolinamide
  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：

  4-氯-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 4-chloro-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

• Pd(II)-Catalyzed, Picolinamide-Assisted, <i>Z</i>-Selective γ-Arylation of Allylamines To Construct <i>Z</i>-Cinnamylamines
  作者：Ramarao Parella、Srinivasarao Arulananda Babu

  DOI：10.1021/acs.joc.7b00535

  日期：2017.7.7

  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.