2017 Fiscal Year Annual Research Report
Ｃ（ｓｐ３）－Ｈ及びＣ（ｓｐ）－Ｈ結合活性化を経るアルキニル化反応の開発．
| Project/Area Number |
16J11354
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| Research Institution | Kyoto University |
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Principal Investigator |
Zhao Qiang 京都大学, 工学研究科, 特別研究員(DC1)
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| Project Period (FY) |
2016-04-22 – 2019-03-31
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| Keywords | carbene / triazole / acceptor/acceptor / arene compounds / enaminones |
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| Outline of Annual Research Achievements |
we have designed and synthesized a new kind of triazole which possessing a unique reactivity with simple unactivated arene compounds. The new developed model triazole is named “4-acyl-1-mesyl-1,2,3-triazole”. We found that it could be generated acceptor/acceptor rhodium carbene complex in the presence of rhodium catalyst. The generated acceptor/acceptor rhodium carbene complex could react with unactivated simple arene compounds, leading to the formation of enaminones. Interestingly, the reaction takes place exclusively with the aromatic C(sp2)-H bonds in the presence of benzylic C(sp3)-H bonds. We also did some experiments to probe the reaction mechanisms. An electrophilic aromatic substitution pathway via a zwitterionic intermediate might be the real reaction mechanism.
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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
We have sucessfully synthesized a new kind of triazole named “4-acyl-1-mesyl-1,2,3-triazole” which could be used as acceptor/acceptor carbene precursor. We found this new synthesized triazole could be generated acceptor/acceptor rhodium carbene complex in the presence of rhodium catalyst. The generated acceptor/acceptor rhodium carbene complex could react with unactivated simple arene compounds, leading to the formation of enaminones. Interestingly, the reaction takes place exclusively with the aromatic C(sp2)-H bonds in the presence of benzylic C(sp3)-H bonds.
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| Strategy for Future Research Activity |
In the following year, we are going to study the intramolecular reactions using acceptor/acceptor carbene precursors. we also want to develop new reactions using the strategy of in-situ generation of acceptor/acceptor carbene complex from 4-acyl-1-sulfonyl-1,2,3-triazoles. We hope we can develop unique new reactions using our new developed strategy which can’t be reached by using traditional donor/acceptor carbenes generated from triazoles.
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Research Products
(4 results)
