| Project/Area Number |
26870079
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| Research Category |
Grant-in-Aid for Young Scientists (B)
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| Allocation Type | Multi-year Fund |
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| Research Field |
Synthetic chemistry
Organic chemistry
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| Research Institution | University of Tsukuba |
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Principal Investigator |
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| Project Period (FY) |
2014-04-01 – 2016-03-31
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| Project Status |
Completed (Fiscal Year 2015)
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| Budget Amount *help |
¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2014: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
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| Keywords | 有機合成化学 / フッ素 / 遷移金属触媒 / 炭素-フッ素結合活性化 / フルオロアルケン / 脱離 |
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| Outline of Final Research Achievements |
I achieved vinylic and allylic C-F bond activation based on beta- and alpha-fluorine elimination from nickelacycle intermediates.
I have developed two types of defluorinative coupling reactions of 2-trifluoromethyl-1-alkenes and alkynes via beta-fluorine elimination from nickelacycles. Addition of Et3SiH enabled a catalytic synthesis of 1,1-difluoro-1,4-dienes, while diboron compounds afforded 2-fluorocyclopentadienes via cleavage of two C-F bonds in a trifluoromethyl group. In both reactions, beta-fluorine elimination from the intermediary nickeracyclopentenes served as a key elementary step. I have also achieved nickel-catalyzed [2+2+2] cyclization of 1,1-difluoroethylene and alkynes via sequential alpha-fluorine and beta-hydrogen elimination, which provides a direct method for the synthesis of fluoroarenes. An alkylborate reagent effectively promoted its catalytic reaction.
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