| Project/Area Number |
26860010
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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 |
Chemical pharmacy
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| Research Institution | The University of Tokyo |
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Principal Investigator |
HIRANO KEIICHI 東京大学, 薬学研究科(研究院), 助教 (40633392)
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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 |
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
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| Keywords | パーフルオロアルキル化 / パーフルオロアリール化 / フッ素 / 亜鉛 / ハロゲンー金属交換 / ハロゲンー亜鉛交換反応 / ジアルキル亜鉛 / 官能基選択性 / DFT計算 / 機能性分子 |
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| Outline of Final Research Achievements |
We developed facile and efficient methods for preparation of RF-zinc species via halogen-zinc exchange between RF-X and dialkylzincs activated by Lewis bases. A stable RF-zincate, RFZn(Cl)MeLi, is generated by using LiCl as an activator and this zinc reagent efficiently perfluoroalkylates various carbonyl compounds at rt. Use of DMPU as an activator forms even more thermally stable RF-zinc, RFZnR(dmpu), and this zinc reagent participates in copper-catalyzed cross-coupling with aryl halides at 120°C. The excellent thermal stability of RF-zinc reagents compares favorably with the Li- and Mg-counterparts, which require cryogenic reaction conditions, and will certainly find further applications. Moreover, we have discovered the allylic polyfluoroarylation reaction of allylic bromides using ArF-Zn activated by phosphine oxides.
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