2020 Fiscal Year Final Research Report
Generalization and application of vinylidene rearrangement of disubstituted alkynes
| Project/Area Number |
18K05154
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Multi-year Fund |
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| Section | 一般 |
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| Review Section |
Basic Section 34010:Inorganic/coordination chemistry-related
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| Research Institution | Chuo University |
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Principal Investigator |
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| Co-Investigator(Kenkyū-buntansha) |
桑原 拓也 中央大学, 理工学部, 助教 (60768654)
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| Project Period (FY) |
2018-04-01 – 2021-03-31
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| Keywords | ビニリデン転位 / ルテニウム / モリブデン / イリジウム / ヘテロ元素 / 結晶二色性 |
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| Outline of Final Research Achievements |
This studty aimed at development of (1) novel metal complex systems that promote vinylidene rearrangement of carbon-disubstituted internal alkynes and (2) vinylidene rearrangement of heteroatom-substituted internal alkynes, especially those with group 15 and 16 substituents. Thus, we have discovered that [(C7H7)MoBr(dppe)] promotes vinylidene rearrangement of internal keto-alkynes in the presence of NaBArF4. On the other hand, P-, S-, and N-substituted internal alkynes such as alkynylphosphonates and alkynyl sulphides were found to be transformed into the vinylidene complexes at [CpRu(dppe)]+, [CpFe(dppe)]+, and [Cp*IrCl(PPh3)]+, and some of the complexes could be converted back to the alkyne on reactions with PPh3. In addition, some of the ruthenium vinylidene complexes derived from alkynylphosphonates and alkynyl sulfones exhibited crystallochromatic phenomena, and the origin of the dichromism was discussed on the basis of the TD-DFT calculations and X-ray diffraction studies.
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| Free Research Field |
有機金属化学
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| Academic Significance and Societal Importance of the Research Achievements |
アルキン錯体からビニリデン錯体を生成するビニリデン転位は、有機合成にも広く応用される重要な反応であるが、従来末端アルキンのみで実施可能とされてきた。我々は近年、炭素置換基を2つ持つ二置換アルキンでも、ビニリデン転位が可能であることを示しているが、まだ例は少ない。本研究では、モリブデンやイリジウムにも内部アルキンのビニリデン転位が可能な金属錯体系を拡張することに成功し、また従来ほとんど知見のなかった15・16族元素の置換基を持つ二置換アルキンのビニリデン転位も見出すことができた。これにより、ビニリデン転位が遷移金属錯体上において一般性の高い反応であることを実証できた。
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