| Project/Area Number |
18K19070
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| Research Category |
Grant-in-Aid for Challenging Research (Exploratory)
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| Allocation Type | Multi-year Fund |
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| Review Section |
Medium-sized Section 33:Organic chemistry and related fields
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
Kuwata Shigeki 東京工業大学, 物質理工学院, 准教授 (10292781)
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| Project Period (FY) |
2018-06-29 – 2021-03-31
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| Project Status |
Completed (Fiscal Year 2020)
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| Budget Amount *help |
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2020: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Fiscal Year 2019: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
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| Keywords | アンモニア / アミン / 均一系触媒 / 金属-配位子協奏機能 / 金属ー配位子協奏機能 |
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| Outline of Final Research Achievements |
In order to realize the catalytic synthesis of nitrogen-containing organic compounds from ammonia, we focused on metal-ligand bifunctional catalysts, which can cleave the N-H bond of ammonia and form C-N bonds effectively. We found that amido complexes of ruthenium and iridium react with ammonia, leading to intramolecular amination of to a C-F bond. In addition, metal complexes with different Bronsted acidity of the proton-responsive site on the ligand, such as dihydropyridylidene and trifluoromethylpyrazole ruthenium complexes, were newly synthesized to improve the activation efficiency of ammonia. Although these complexes promote the N-H bond cleavage of ammonia, the trifluoromethylpyrazole complex catalyzed isomerization of propargylic alcohols to enones.
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| Academic Significance and Societal Importance of the Research Achievements |
基幹化成品として入手容易なアンモニアから、医農薬、機能性材料等の原料として幅広く利用されている含窒素化合物、とりわけ第1級アミン類を直接合成する反応は工業プロセス、精密有機合成の両面で大きな意義をもつ。本研究の成果は、その実現のための基礎的な知見を与えるともに、また、金属ー配位子協働作用に分子活性化、変換という方法論の進展につながるものである。
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