C-H Functionalization Using Radical Cation Pools

2014 Fiscal Year Final Research Report

• Project/Area Number: 25620081
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: YOSHIDA Junichi 京都大学, 工学(系)研究科(研究院), 教授 (30127170)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Keywords: ラジカルカチオン / 電解酸化 / C-H官能基化

Outline of Final Research Achievements

We developed a new method for introduction of nitrogen functionalities to aromatic compounds by electrochemical oxidation (C-H amination). The electrochemical oxidation of aromatic compounds in the presence of pyridine leads to the formation of N-arylpyridinium ions. Treatment of N-arylpyridinium ions with piperidine gives the corresponding aniline derivatives. The key to the success of the present method is the generation of cationic intermediates which does not suffer from overoxidation by the electrochemical reaction. Based on a similar reaction design based on the advantage of the cationic intermediates, the electrochemical C－N coupling reactions of imidazoles with aromatic and benzylic compounds was also developed. The anodic oxidation of a substrate in the presence of N-methylsulfonylimidazole gives the imidazolium intermediate, treatment of which with piperidine leads to the formation of the desired products.

Free Research Field

化学