| 研究課題/領域番号 |
18F18777
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| 研究機関 | 国立研究開発法人理化学研究所 |
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研究代表者 |
イリエシュ ラウレアン 国立研究開発法人理化学研究所, 環境資源科学研究センター, チームリーダー (40569951)
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| 研究分担者 |
KULESHOVA OLENA 国立研究開発法人理化学研究所, 環境資源科学研究センター, 外国人特別研究員
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| 研究期間 (年度) |
2018-11-09 – 2021-03-31
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| キーワード | 有機合成 |
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| 研究実績の概要 |
The proposed research aims at the development of regioselective functionalization of simple arenes, through the design of bifunctional ligands capable of recognizing the substrate intermolecularly through non-covalent interactions such as pi-pi or cation-pi interaction.
During FY2019, a series of bifunctional ligands were designed and synthesized. Thus, a series a terpyridine-type molecules were substituted with various arene groups, based on the hypothesis that the terpyridine unit will act as a ligand to the metal catalyst, and the arene groups will bring an arene substrate close to the metal center through pi-pi interaction. Also, arene groups substituted with hydroxy groups were also introduced, in order to bear a cation for recognizing the arene substrate through cation-pi interaction. The ligands were tested for several reactions such as cobalt- or iridium-catalyzed arene borylation.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
2: おおむね順調に進展している
理由
The JSPS researcher arrived in Japan on November 1, 2018. After accommodating with the laboratory, undergoing the safety training and other required preparations, she started working on the project at the beginning of January. Despite this late start, she immediately achieved a good progress: after getting used with DFT calculation, she designed a series of ligands, and started synthesizing them, while also testing them for cobalt- and iridium-catalyzed reactions.
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| 今後の研究の推進方策 |
During FY2019, we will continue the design and synthesis of bifunctional ligands bearing a metal-coordination unit (terpyridine and related molecules), appended with one or two units that recognize an arene substrate through non-covalent interactions such as pi-pi or cation-pi interaction. Based on the knowledge gained in FY2018, the ligand design will be refined, for example the recognition units will be more flexible, or appended at further away positions than ortho- or para- relative to nitrogens.
The ligands will be investigated for transition-metal-catalyzed C-H activation of simple arenes. Initial studies will be performed with a solvent amount of arene, studying a possible acceleration effect due to the non-covalent interactions. The accelerating effect will be then extrapolated to reaction using one equivalent of substrate, especially targeting difficult substrates such as electronically- or sterically-disfavored arenes. Based on initial results from FY2018, the first choice for the model reaction will be cobalt- and iridium-catalyzed borylation of arenes.
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