2014 Fiscal Year Final Research Report
Ketene formation via catalytic oxygen-atom transfer to vinylidene carbene
| Project/Area Number |
25620077
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| Research Category |
Grant-in-Aid for Challenging Exploratory Research
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| Allocation Type | Multi-year Fund |
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| Research Field |
Synthetic chemistry
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| Research Institution | Nagoya University |
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Principal Investigator |
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| Project Period (FY) |
2013-04-01 – 2015-03-31
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| Keywords | 遷移金属触媒 / ルテニウム錯体 / アルキン / 多環芳香族化合物 / 複素環化合物 |
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| Outline of Final Research Achievements |
In the presence of a dicationic ruthenium complex with p-cymene and triphenylphosphine ligands, 2-ethynylbiaryls underwent cycloisomerization to afford phenanthrenes. Heterocyclic anolog of 2-ethynylbiaryls containing furan, thiophene, and pyrrole rings were also transformed into heteropolyaromatic compounds in higher yields. DFT calculations of model systems suggested that the cycloisomerization proceeded with the Friedel-Crfats type cyclization without intermediacy of an expected vinylidene carbene complex.
Furthermore, it was found that a cationic ruthenium complex catalyzed the transfer-oxygenative [2+2+1] cycloaddition of 1,6-diynes with at least one trimethylsilyl terminal, affording bicyclic silylfurans. As the oxygen-atom donor, nitrons proved to be more effective than the previously used DMSO.
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| Free Research Field |
有機合成
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