| Project/Area Number |
62470079
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
有機工業化学
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
NAKAI Takeshi Faculty of Engineering, Tokyo Institute of Tcchnology, 工学部, 教授 (90016717)
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| Co-Investigator(Kenkyū-buntansha) |
MIKAMI Koichi Faculty of Engineering, Tokyo Institute of Tcchnology, 工学部, 助教授 (10157448)
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| Project Period (FY) |
1987 – 1988
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| Project Status |
Completed (Fiscal Year 1988)
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| Budget Amount *help |
¥5,700,000 (Direct Cost: ¥5,700,000)
Fiscal Year 1988: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1987: ¥3,600,000 (Direct Cost: ¥3,600,000)
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| Keywords | Fluorine Chemistry / Perfluoro-enolate / Enolate / Aldol Reaction / Ambident Reactivity / Polyfluoro-enolate / ペルフルオロオレフィン / リチウムペルフルオロプロペノラート / 異常求電子反応性 |
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| Research Abstract |
In contrast to the central position of enolate chemistry in synthetic organic chemistry, perfluorinated enolate (F-enolate) chemistry, despite its great potential, remains unexplored. In the present research project, we have successfully developed a facile and general method for selective generation of metal F-enolate such as CF_3C(OM)=CF_2 and R_fC(OM)=CFCF_3 (M=Li, Na, and K) from polyfluorinated alcohols (R_fCH(OH)R_f'). The "dehydrofluorinative" generation metod has been shown to exhibit a high level of regioselection and/or stereoselection in the F-enolate formation.
Furthermore the F-enolate thus generated have been demonstrated to exhibit a unique and wide spectrum of reactivity toward both electrophilic and nucleophilic reagents. Of particular interest is that the F-enolates show not only the normal enolate reactivities (O- and C-nucleophilicity) including the aldol reactivity, but also the "unusual" electrophlic reactivity toward organometallic reagents such as rli and RM_gX to generate the -alkylated F-enolates (polyfluorinated enolate) such as R@>D2f@>D2C(OM)=CF-Bu. Finally, the unique reactivities of such polyfluorinated enolate have been defined.
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