| 研究課題/領域番号 |
14F04035
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| 研究機関 | 名古屋大学 |
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研究代表者 |
大井 貴史 名古屋大学, トランスフォーマティブ生命分子研究所, 教授 (80271708)
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| 研究分担者 |
CORBETT Michael 名古屋大学, トランスフォーマティブ生命分子研究所, 外国人特別研究員
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| 研究期間 (年度) |
2014-04-25 – 2016-03-31
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| キーワード | 1,2,3-triazoliums / ion pairs / photosensitizers / bond homolysis / radical reactions |
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| 研究実績の概要 |
At the onset of our research efforts, we prepared chiral bifunctional triazole-containing catalysts, where a carbonyl was inserted as a lynchpin to bridge the triazole and amide functionalities. Although these catalysts exhibited poor reactivity as chiral ion-pair catalysts, we serendipitously found that their absorption spectra exhibited strong absorption in the near-ultraviolet range. Upon irradiation of these triazole ketones with 365-nm wavelength light, we observed that they were capable of serving as H-bond abstractors and efficiently promoted the radical addition of acetals and primary/secondary alcohols to various Michael acceptors. Given this observation, we turned our research focus towards the design and synthesis of novel carbonyl compounds that can serve as photocatalysts to mediate radical reactions. Analysis of the activity/structure relationships of these carbonyl compounds directed our research towards the identification of a new class of aryl ketones that can serve as even more reactive H-bond abstractors than commonly employed catalysts in the literature.
Concurrently, we have also realized that modified thioxanthone and acridone structures serve as viable photosensitizers in energy transfer reactions. The excited triplet state of these carbonyl-containing compounds can be effectively transferred to other molecules containing weak C-X and N-O bonds leading to bond homolysis under mild visible light conditions. Although this work is still at a preliminary stage, it represents a promising point from which a wealth of valuable chemistry can be developed.
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| 現在までの達成度 (区分) |
現在までの達成度 (区分)
1: 当初の計画以上に進展している
理由
Although we have not been able to actively pursue the research originally proposed to the JSPS Postdoctoral Fellowship program, our initial efforts have led us to the identification of several new research areas that can potentially have a large impact in the scientific community and will be an area of research we will continue to explore. Therefore, we consider our current level of research to be more than satisfactory.
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| 今後の研究の推進方策 |
Given our scientific findings during the previous fiscal year, we will continue to pursue our new research program aggressively by focusing on several key goals. We will seek to identify a chiral photocatalyst that can be employed in visible-light mediated alkene difunctionalization reactions through the homolytic cleavage of labile bonds though energy transfer pathways. We will also continue to investigate the design and synthesis of chiral aryl ketone catalysts that can serve as H-bond abstractors under near-ultraviolet light irradiation for the asymmetric hydroformylation of electron-deficient alkenes. Thorough mechanistic studies will compliment these research goals providing valuable information for effective catalyst and reaction design.
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