Development of Fe-catalyzed radical type-arylartion

2014 Fiscal Year Final Research Report

• Project/Area Number: 25620085
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Hiroshima University
• Principal Investigator: KOMEYAMA Kimihiro 広島大学, 工学(系)研究科(研究院), 助教 (80432681)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Keywords: 鉄 / ラジカル / カップリング / ビアリール / ヘテロ芳香族化合物 / 芳香族ボロン酸

Outline of Final Research Achievements

We found that iron reagents like FeSO4 was effective reagent for the generation of aryl radicals from arylboronic acids. For its synthetic applications, we achieved a direct arylation of benzoquinones with the generated aryl radicals from the bronco acids, in which a diverse set of monoarylated benzoquinones were obtained in good yields. In addition, addition of ascorbic acids to the reaction media or replacement of benzoquinones by hydroquinones made the iron-mediated arylation change to catalytic reaction. Furthermore, we tried to a direct arylation of heteroarenes by means of iron-mediated aryl radical generation, wherein many type of heteroarenes such as pyridines, pyridine, pyrimidines could participated in the arylation. To gain a insight of the radical generation process, we investigated the process by DFT calculation. As a results, electron density on the aryl ring of moronic acids strongly depended on the efficiency of the radical generation process.

Free Research Field

有機合成化学、有機金属化学