3-methoxy-2-methyl-9-(pyridin-2-yl)-9H-carbazole | 1416353-95-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 3-methoxy-2-methyl-9-(pyridin-2-yl)-9H-carbazole
• CAS: 1416353-95-1
• 化学式: C₁₉H₁₆N₂O
• 分子量: 288.349
• InChiKey: KQTWUPQBQFCJKF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  27.05
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  3-methoxy-2-methyl-9-(pyridin-2-yl)-9H-carbazole 在 palladium diacetate 、 silver nitrate 、 对苯醌 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 、 叔丁醇 为溶剂， 反应 60.0h， 生成 6-methoxy-7-methyl-1-phenyl-9H-carbazole
  参考文献：
  名称：

  Direct Ortho Arylation of 9-(Pyridin-2-yl)-9H-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation

  摘要：

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.

  DOI：

  10.1021/om301071m
• 作为产物：
  描述：

  N-(4-methoxy-3-methylphenyl)pyridin-2-amine 在 sodium persulfate 、 对苯醌 作用下， 以 1,4-二氧六环 、 二氯甲烷 为溶剂， 反应 14.0h， 生成 3-methoxy-2-methyl-9-(pyridin-2-yl)-9H-carbazole
  参考文献：
  名称：

  Direct Ortho Arylation of 9-(Pyridin-2-yl)-9H-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation

  摘要：

  A one-pot synthesis of ortho-arylated 9-(pyridin-2-yl)-9H-carbazoles via C-H bond activation is presented. Silver nitrate and tert-butyl alcohol were found to be the best oxidant and solvent for the process, respectively. The product yields are from modest to excellent, and the reaction showed sufficient functional group tolerance. p-Benzoquinone served as an important ligand for the transmetalation and reductive elimination steps in the catalytic process. The key intermediate of the reaction, a 9-(pyridin-2-yl)-9H-carbazole palladacycle, was isolated, and its structure was unequivocally confirmed by X-ray crystallography. No kinetic isotope effect (k(H)/k(D) = 1.00 +/- 0.17) for the C-H bond activation step was observed. In addition, a Hammett experiment gave a negative rho value, -2.16 +/- 0.02. The directing group, pyridinyl, was demonstrated to be a removable functional group. Finally, a rational catalytic mechanism is presented on the basis of all experimental evidence.

  DOI：

  10.1021/om301071m

文献信息

• Site-Selective Aerobic C–H Monoacylation of Carbazoles Using Palladium Catalysis
  作者：Subhadip Maiti、Tirtha Mandal、Barada Prasanna Dash、Jyotirmayee Dash

  DOI：10.1021/acs.joc.0c01746

  日期：2021.1.15

  remarkably general palladium-catalyzed monoacylation of carbazoles using toluene derivatives playing the dual role of acyl source and organic solvent. The method uses NHPI as the cocatalyst and oxygen as the sole oxidant. Interestingly, the acylation of monosubstituted N-pyridylcarbazoles takes place regioselectively at the C-8 position. The scope of the method is explored using aldehyde as the acyl source

  这篇手稿描述了使用甲苯衍生物开发的一种非常通用的钯催化咔唑单酰化，甲苯衍生物起到了酰基源和有机溶剂的双重作用。该方法使用NHPI作为助催化剂，氧气作为唯一的氧化剂。有趣的是，单取代的N-吡啶基咔唑的酰化在 C-8 位区域选择性地发生。使用醛作为酰基源探索了该方法的范围。这种高度位点选择性酰化通过一个激进的过程进行。