| Project/Area Number |
18K06583
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Review Section |
Basic Section 47010:Pharmaceutical chemistry and drug development sciences-related
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| Research Institution | Kumamoto University |
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Principal Investigator |
Ando Shin 熊本大学, 大学院生命科学研究部(薬), 助教 (00622599)
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| Project Period (FY) |
2018-04-01 – 2021-03-31
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| Project Status |
Completed (Fiscal Year 2020)
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| Budget Amount *help |
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
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| Keywords | 有機化学 / 配位子 / 遷移金属触媒 / 錯体 / 含窒素複素環式カルベン / N-ヘテロ環状カルベン |
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| Outline of Final Research Achievements |
N-heterocyclic carbene (NHC) is widely applied as a useful ligand, and imidazol-2-ylidene and imidazolin-2-ylidene became the standard heterocyclic form, and bulky substituents have commonly been introduced on the nitrogen(s) adjacent to carbenic carbons. Our group previously developed NHCs equipped with non-carbenic carbons with a bicyclic architecture that gives them unique steric properties. In this study, we synthesized a novel type of NHC ligand that possesses a bicyclo[2.2.1]heptane architecture, and we found that an aromatic ring on this bicyclic architecture has a characteristic effect. Additionally, we calculated TEP and %VBur values to evaluate the electronic and steric features of our NHC ligands, and, as a result, the electronic influences from the derivatization were found to be negligible. The steric environments existing at relatively long distances from the bound metals also exerted a considerable amount of influence over the catalytic properties.
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| Academic Significance and Societal Importance of the Research Achievements |
金属を触媒として用いる際に金属塩の可溶化や触媒機能の調製に配位子は欠かせない存在である。主に配位子の立体的性質と金属に対する電子供与が触媒の機能に影響することが知られており、配位子を変えてこれらの性質を調節することが望む化学変換に対して高活性な金属触媒系を確立するために行われる。本研究では新たにビシクロ骨格を備えたNHC配位子を合成し、従来にない遠位の置換基を利用した新戦略の確立を目指し、より安定性や活性に優れた金属錯体を得るために必要な構造的要因を明らかとした。更なる検討によって新たな高活性金属触媒の開発につながるものと期待する。
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