2021 Fiscal Year Final Research Report
Creation of Transition Metal Difluorocarbene Complexes and Their Application to Catalytic Syntheses of Organofluorine Compounds
| Project/Area Number |
20K21186
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| Research Category |
Grant-in-Aid for Challenging Research (Exploratory)
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| Allocation Type | Multi-year Fund |
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| Review Section |
Medium-sized Section 33:Organic chemistry and related fields
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| Research Institution | University of Tsukuba |
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Principal Investigator |
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| Project Period (FY) |
2020-07-30 – 2022-03-31
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| Keywords | カルベン / フッ素 / 触媒 / チオフェン / フラン / ジフルオロアルケン / 金 |
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| Outline of Final Research Achievements |
Fluorine-substituted transition metal carbene complexes are promising intermediates for the synthesis of organofluorine compounds. Thus, the preparation and utilization of the complexes were investigated. 1,1-Difluoroallenes were treated with aldehydes in the presence of a gold(I) catalyst. [3 + 2] Cycloaddition proceeded and the expected gold(I) carbene complexes bearing a tetrahydrofuran ring were generated. beta-Hydrogen migration and subsequent dehydrofluorination of the complexes facilitated the regioselective synthesis of 2-fluorofurans. The utilization of free difluorocarbene was also investigated. (Regioselective) syntheses of 1,1-difluoroalkenes and 2-fluorothiophenes by the reaction with thiocarbonyl compounds were developed.
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| Free Research Field |
有機合成化学、有機フッ素化学
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| Academic Significance and Societal Importance of the Research Achievements |
フッ素置換遷移金属カルベン錯体の性質には、学術的な観点から興味が持たれていた。しかし実際には調製例自体が少なく、性質は未知であった。本研究課題により、ジフルオロアレンの付加環化でフッ素置換環状金(I)カルベン錯体が調製できること、また、発生した錯体はβ-水素移動を起こすことが明らかになった。また、併せて見出した遊離ジフルオロカルベンの反応性も、これまでに知見が少なく、今後これを配位子として利用する際に重要な情報となる。我々が合成法を確立したフルオロフランやフルオロチオフェン、ジフルオロアルケンは、いずれも生理活性化合物や合成中間体として有用なものであり、今後医農薬開発等の領域に貢献できる。
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