| Project/Area Number |
11450340
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| Research Category |
Grant-in-Aid for Scientific Research (B).
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
有機工業化学
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| Research Institution | Osaka University |
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Principal Investigator |
CHATANI Naoto Osaka University, Graduate School of Engineering-Associate Professor, 大学院・工学研究科, 助教授 (30171953)
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| Project Period (FY) |
1999 – 2000
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| Project Status |
Completed (Fiscal Year 2000)
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| Budget Amount *help |
¥12,900,000 (Direct Cost: ¥12,900,000)
Fiscal Year 2000: ¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 1999: ¥9,400,000 (Direct Cost: ¥9,400,000)
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| Keywords | carbonylation / carbon-hydrogen bond / carbon monoxide / ruthenium / decarbonylation / coordination / 炭素-水素結合切断 / 炭素-炭素結合切断 |
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| Research Abstract |
The purpose of Grant-in-Aid for Scientific Research (B) was the development of direct carbonylation at C-H bonds and the development of new catalytic reactions based on the knowledge obtained from the research on the direct carbonylation reactions. As a result, we found the following results.
We have already reported the ruthenium-catalyzed carbonylation at C-H bonds α to the sp^2 nitrogen in the reaction of imidazoles with CO and olefins. We found that other five-membered N-heteroaromatic compounds, such as oxazoles, thiazoles, and pyrazoles can also be used for the carbonylation reaction. The reactivity of the substrates corresponds to the pKa of the conjugate acid of the substrates. The higher pKa of the substrates, the higher is the reactivity.
We have already reported the ruthenium-catalyzed carbonylation at C-H bond ortho position in the reaction of pyridylbenzenes with CO and olefins, in which the pyridine ring acts as a directing group. It is found that an oxazoline ring can also act as a directing group for the carbonylation reaction. The reaction can proceed even at 1 atm of CO in some substrates.
All of carbonylation reactions we found thus far are carbonylation at sp^2 C-H bonds. It is found that sp^3 C-H bonds α to the nitrogen atom in alkylamines can be carbonylated in the presence of a rhodium complex as the catalyst.
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