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

与烯酸酯化学在合成有机化学中的中心地位相反，全氟烯酸酯（f -烯酸酯）化学尽管潜力巨大，但仍未得到开发。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，用于从多氟化醇（R_fCH(OH)R_f'）中选择性生成CF_3C(OM)=CF_2和R_fC(OM)=CFCF_3 （M=Li, Na， K）等金属f -烯醇酯。“脱氢氟化”生成方法已被证明在f -烯酸酯形成中表现出高水平的区域选择和/或立体选择。此外，由此产生的f -烯酸酯已被证明对亲电和亲核试剂都具有独特的广谱反应性。特别令人感兴趣的是，f -烯醇酸酯不仅表现出正常的烯醇酸酯反应性（亲O核性和亲c核性），包括醛醇反应性，而且对有机金属试剂（如rli和RM_gX）也表现出“不寻常的”亲电反应性，生成-烷基化f -烯醇酸酯（多氟化烯醇酸酯），如R@>D2f@>D2C(OM)=CF-Bu。最后，定义了这种多氟化烯醇酯的独特反应活性。

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.