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比，全氟烯酸酯(F-enode)化学尽管具有巨大的潜力，但仍未被开发。在本研究项目中，我们成功地开发了一种从多氟醇(R_FCH(OH)R_f‘)中选择生成金属F-烯酸酯的简便而通用的方法，如CF_3C(OM)=CF_2和R_FC(OM)=CFCF_3(M=Li，Na，K)。脱氢氟代方法在F-烯酸酯类化合物中表现出很高的区域选择性和/或立体选择性。此外，由此产生的F-烯类化合物对亲电试剂和亲核试剂都表现出独特的广谱反应活性。特别值得注意的是，F-烯醇酸盐不仅表现出正常的烯醇反应性(O-和C-亲核性)，包括羟醛反应性，而且还表现出对有机金属试剂如RLi和Rm_GX的“不寻常”的电泳性反应，以生成-烷基化的F-烯醇酸盐(多氟烯醇酸盐)，如R@&gt；D2f@&gt；D2C(OM)=CF-Bu。最后，确定了这种多氟烯醇酸的独特反应性。

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.