3-nitro-9-(pyridin-2-yl)-9H-carbazole | 1352932-16-1

• 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-nitro-9-(pyridin-2-yl)-9H-carbazole
• 英文别名: 3-Nitro-9-pyridin-2-ylcarbazole；3-nitro-9-pyridin-2-ylcarbazole
• CAS: 1352932-16-1
• 化学式: C₁₇H₁₁N₃O₂
• 分子量: 289.293
• InChiKey: WWMUIANMFKTCOG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  63.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-nitro-9-(pyridin-2-yl)-9H-carbazole 、 苯基三氟硼酸钾 在 palladium diacetate 、 silver nitrate 、 对苯醌 作用下， 以 叔丁醇 为溶剂， 反应 24.0h， 生成 6-nitro-1-phenyl-9-(pyridin-2-yl)-9H-carbazole 、 3-nitro-1-phenyl-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
• 作为产物：
  描述：

  4-硝基苯胺 在 tris-(dibenzylideneacetone)dipalladium(0) 、 potassium tert-butylate 、 silver(I) acetate 、 palladium diacetate 、 双(2-二苯基磷苯基)醚 、 对苯醌 作用下， 以 1,4-二氧六环 、 水 、 乙酸乙酯 、 甲苯 为溶剂， 生成 3-nitro-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

• Substituent Electronic Effects Govern Direct Intramolecular C–N Cyclization of <i>N</i>-(Biphenyl)pyridin-2-amines Induced by Hypervalent Iodine(III) Reagents
  作者：Jean-Ho Chu、Wen-Ting Hsu、Yi-Hua Wu、Meng-Fan Chiang、Nan-Hai Hsu、Hao-Ping Huang、Ming-Jung Wu

  DOI：10.1021/jo501822m

  日期：2014.12.5

  The hypervalent iodine(III) reagent-induced the direct intramolecular C–N cyclization of N-(biphenyl)pyridin-2-amines to 6-arylbenzimidazoles and N-pyridinyl-9H-carbazoles is presented. The substituent electronic effects governing the formation of benzimidazoles and carbazoles from the reaction of N-(biphenyl)pyridin-2-amines with hypervalent iodine(III) reagents is investigated. Radical trapping and

  提出了高价碘（III）试剂诱导的N-（联苯基）吡啶-2-胺直接分子内C–N环化为6-芳基苯并咪唑和N-吡啶基-9 H-咔唑的方法。研究了N-（联苯基）吡啶-2-胺与高价碘（III）试剂反应时支配苯并咪唑和咔唑形成的取代基电子效应。进行了自由基捕获和紫外可见光谱检测阳离子自由基的实验。提出了这些反应的合理机制。还介绍了基于取代基电子效应的N-（联苯）乙酰胺的选择性分子内C–N和C–O环化。
• Palladium(II)-Catalyzed One-Pot Syntheses of 9-(Pyridin-2-yl)-9H-carbazoles through a Tandem CH Activation/CX (X=C or N) Formation Process
  作者：Jean-Ho Chu、Pi-Shan Lin、Ya-Ming Lee、Wei-Ting Shen、Ming-Jung Wu

  DOI：10.1002/chem.201101528

  日期：2011.11.25

  A new one‐pot synthesis of 9‐(pyridin‐2‐yl)‐9H‐carbazoles through the simultaneous CH activation and palladium(II)‐catalyzed cross‐coupling of N‐phenylpyridin‐2‐amines with potassium aryltrifluoroborates is presented. Silver acetate and 1,4‐dioxane proved to be the best oxidant and solvent, respectively. The product yields fluctuated from modest to excellent and the reaction showed sufficient functional

  通过同时的CH活化和钯（II）催化的N-苯基吡啶-2-胺与芳基三氟硼酸钾的交叉偶联，新的一锅合成9-（吡啶-2-基）-9 H-咔唑的方法是提出了。醋酸银和1,4-二恶烷分别被证明是最好的氧化剂和溶剂。产物收率从适中波动至优异，反应显示出足够的官能团耐受性。对苯醌是催化过程中金属转移和还原消除步骤的重要配体。第一和第二次CH活化/ C的动力学同位素效应（k H / k D）。 C或C  ñ形成步骤测量为分别2.14和1.18，。最后，基于所有实验证据提出了合理的催化机理。
• Direct Ortho Arylation of 9-(Pyridin-2-yl)-9<i>H</i>-carbazoles Bearing a Removable Directing Group via Palladium(II)-Catalyzed C–H Bond Activation
  作者：Jean-Ho Chu、Chung-Chiu Wu、Deng-Hsiang Chang、Ya-Ming Lee、Ming-Jung Wu

  DOI：10.1021/om301071m

  日期：2013.1.14

  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.