| Project/Area Number |
22KJ0075
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| Project/Area Number (Other) |
22J11710 (2022)
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| Research Category |
Grant-in-Aid for JSPS Fellows
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| Allocation Type | Multi-year Fund (2023)
Single-year Grants (2022) |
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| Section | 国内 |
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| Review Section |
Basic Section 33020:Synthetic organic chemistry-related
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| Research Institution | Hokkaido University |
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Principal Investigator |
游 震生 北海道大学, 大学院総合化学院, 特別研究員(DC2)
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| Project Period (FY) |
2023-03-08 – 2024-03-31
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| Project Status |
Declined (Fiscal Year 2023)
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| Budget Amount *help |
¥1,700,000 (Direct Cost: ¥1,700,000)
Fiscal Year 2023: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2022: ¥900,000 (Direct Cost: ¥900,000)
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| Keywords | Organophosphorus reagent / Aryl fluorides / Reaction mechanism / DFT calculation |
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| Outline of Research at the Start |
Although transition-metal (TM) catalysis are broadly used in organic synthesis , most of them are associated with drawbacks due to their limited availability. By contrast, phosphorus is a widely distributed group 15 element possessing an unique biphilic nature. Such a property may arrange a TM-like catalytic cycle. The full catalytic behavior possibility still remains unknown.
This research project aims at developing a phosphorus catalyst containing a TM-like catalytic cycle. A hybrid methodology combining both computational and experimental protocols will be used for the investigation.
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| Outline of Annual Research Achievements |
The initial synthetic plan was the construction of the cage structure by sequential silyl protection, Ullmann coupling, and phosphination. However, the experimental result suggested direct silyl protection of 2-iodophenol was a challenge. Hence, MOMCl was used to protect iodophenol, Ullmann coupling between the protected product and methyl amine delivered the aniline in 37% yield. However, the reaction with PCl3 resulted in a complex mixture, which was thought to be due to in situ deprotection of MOM and the sluggish reactivity with PCl3.
On the other hand, I previously developed a Ni-catalyzed defluorophosphonylation reaction between aryl fluorides and H-phosphonates to produce the corresponding aryl phosphonates . A wide range of aryl fluorides, including electron-rich and electron-neutral ones, were functionalized without the requirement of pre-activation. However, the mechanistic insight, especially the role of phosphorus reagents, was remained unresolved. The target of this project was to reveal the unknown behaviors of phosphorus reagents in catalysis by using computational methods. Mechanistic studies based on both experimental and computational investigations suggested in situ generated KOP(OR)2 could reduce Ni(II) complex to Ni(0) species. Next, dissociation of KOP(OR)2 and association of aryl fluorides generate catalytic species, in which the phosphite forms a strong electron-donating dimeric ligand system for performing C-F oxidative addition in a low energy barrier.
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| Research Progress Status |
翌年度、交付申請を辞退するため、記入しない。
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| Strategy for Future Research Activity |
翌年度、交付申請を辞退するため、記入しない。
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Report
(1 results)
Research Products
(2 results)
