ペルフルオロエノラートの生成と合成的利用に関する研究

全氟烯醇化物的生产及合成利用研究

• 批准号: 62470079
• 负责人: NAKAI Takeshi
• 金额: $ 3.65万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1987
• 资助国家: 日本
• 起止时间: 1987 至 1988
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-62470079/
• 关键词: 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

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.

与化学在合成有机化学中的中心位置相反，尽管具有巨大的潜力，但全氟化（F-层）化学仍未开发。在本研究项目中，我们成功地开发了一种简单而通用的方法，用于选择性地生成金属F-二酸盐，例如CF_3C（OM）= CF_2和R_FC（OM）= CFCF_3（M = Li，Na，Na和K）从polyfluorationed醇（R_FCH（R_FCH（OH）R_F'）中。已证明“脱氢”生成MetoD在F型酸酯形成中表现出高水平的区域选择和/或立体选择。因此，因此已经证明了F-ryale所产生的F-二酸盐表现出对电酚和核碱重新测明的独特而广泛的反应性。 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.最后，已经定义了这种多氟烯的独特反应性。

项目成果

銭承平: 日本化学会第58回春季年会講演予稿集. II. (1989)

Cheng, Chen：第 58 届日本化学会春季年会论文集 II。

銭承平: 日本化学会第56回春季年会講演予稿集. II. 1247 (1988)

Cheng, Chen：日本化学会第 56 届春季年会论文集 II。

銭承平: 日本化学会第54春季年会講演予稿集. II. 1355 (1987)

Cheng, Chen：日本化学会第 54 届春季年会论文集 II。

Takeshi Nakai: "Perfluoro-enolate Chemistry: Facile Generation and Unique Reactivities of Metal F-Propen-2-Olate and Its Homologues" Abstract of 12th International Symposium of Fluorine Chemistry. 302 (1988)

Takeshi Nakai：“全氟烯醇化物化学：金属F-丙烯-2-油酸盐及其同系物的简便生成和独特反应性”第十二届国际氟化学研讨会摘要。

Takeshi Nakai: "Exploration of Perfluoro-enolate Chemistry and Its Synthetic Applications" Reseach Report of Foundation for Development of Chemical Materials. 3. 31-33 (1988)

中井武：《全氟烯醇化物化学及其合成应用的探索》化学材料发展基金会研究报告。