| 配分額 *注記 |
8,320千円 (直接経費: 6,400千円、間接経費: 1,920千円)
2019年度: 4,160千円 (直接経費: 3,200千円、間接経費: 960千円)
2018年度: 4,160千円 (直接経費: 3,200千円、間接経費: 960千円)
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| 研究実績の概要 |
The purpose of this project is the selective functionalization of C(sp3)-H bonds by exploiting a hybrid radical/organometallic reactivity of first row transition metals such as iron, manganese, cobalt, or nickel. We found that an iron salt and deprotonated carbazole form an amidoiron complex that in the presence of an aryl iodide and upon visible light irradiation aminates the alfa position of THF, or the allylic position of an alkene. While synthetically meaningful reaction scope and yield could not be achieved to date, these results demonstrate that the hybrid reactivity of first row transition metals can be initiated by light, instead of the previously used reactive Grignard reagents.
We also discovered a new reactivity of organomolybdenum species, which activated an aryl chloride or fluoride to promote a homocoupling or a cross-coupling reaction. These results are meaningful, because molybdenum is reluctant to react with aromatic halides, and molybdenum-catalyzed coupling of halides has been scarcely reported. We developed a molybdenum-catalyzed reaction of 2-haloaryl ketones, where two substrate molecules react in a cyclative manner to produce a phthalan derivative. The reaction scope and preliminary mechanistic studies were performed, and the manuscript is in preparation for publication.
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