Development of SpiroBipyridine Ligands for Efficient and Selective C-H Activation
Publicly Offered Research
| Project Area | Digitalization-driven Transformative Organic Synthesis (Digi-TOS) |
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| Project/Area Number |
22H05384
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| Research Category |
Grant-in-Aid for Transformative Research Areas (A)
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| Allocation Type | Single-year Grants |
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| Review Section |
Transformative Research Areas, Section (II)
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| Research Institution | Institute of Physical and Chemical Research |
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Principal Investigator |
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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| Project Period (FY) |
2022-06-16 – 2024-03-31
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| Project Status |
Granted (Fiscal Year 2023)
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| Budget Amount *help |
¥7,800,000 (Direct Cost: ¥6,000,000、Indirect Cost: ¥1,800,000)
Fiscal Year 2023: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2022: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
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| Keywords | 有機合成 / organic synthesis |
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| Outline of Research at the Start |
Direct functionalization of simple or complex organic molecules is the most straightforward method to create new chemical space, but these reactions suffer limitations regarding efficiency and selectivity. I plan to use conceptually new spirobipyridine ligands and the power of machine learning to unlock a general strategy to functionalize a target C-H bond in a stoichiometric amount of a simple or complex arene under mild conditions and regio- and chemoselectively.
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| Outline of Annual Research Achievements |
The purpose of this research is the development of new spirobipyridine ligands and of reaction conditions for the efficient and site-selective catalytic functionalization of arenes. During FY2022, we developed a spirobipyridine ligand that greatly accelerates the iridium-catalyzed borylation of arene derivatives, including electron-rich compounds, which are typically less reactive using conventional bipyridine ligands.
Mechanistic investigations by experiment and computations suggested that a non-covalent interaction between a C-H bond of the ligand backbone and the pi electrons of the arene substrate is responsible for the acceleration effect.
We also submitted experimental data into the database of the transformative research area.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
As described at the research summary, an efficient ligand was developed, and a mechanistic analysis was performed to suggest an intriguing non-covalent interaction for reaction acceleration. Moreover, reaction data was submitted for machine learning. These results have been submitted, and the manuscript is under review.
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| Strategy for Future Research Activity |
During FY2023, we plan to strengthen the collaboration with the members of the transformative research area, especially increasing the number of data points for machine learning, collaboration with computation specialists for further understanding of the non-covalent interactions and their effect on reactivity, and the development of supported spirobipyridine ligands for reactions in flow.
We also plan to develop spirobipyridine ligands bearing molecular units that can interact with the substrate through attractive non-covalent interactions, and both accelerate the reaction and control selectivity.
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Report
(1 results)
Research Products
(15 results)
