In this study, we have developed a metal‐mediated synthetic method for incorporating the 1,1,2,2‐tetrafluoroethyl (CF2CF2H) motif into unactivated, electron‐rich alkenyl iodides using cross‐coupling reactions. We discovered that the stable Cu(CF2CF2H)(PPh2Me)3 complex, while unreactive with these substrates, serves as a valuable P‐ligated reservoir for the formation of solvent‐stabilized "ligandless" and reactive CuCF2CF2H species. This transformation occurs upon addition of CuBr, which partially scavenges the P‐ligand in the form of CuBr(PPh2Me)3. The resulting in situ generated solvent stabilized "ligandless" system significantly enhances the reactivity of the complex, particularly towards challenging electron‐rich substrates. This advancement enables the synthesis of HCF2CF2‐glycals, as well as nucleosides/nucleobases and arenes.

中文翻译：

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通过原位生成溶剂稳定的“无配体”CuCF2CF2H实现富电子烯基碘化物的四氟乙基化

在这项研究中，我们开发了一种金属介导的合成方法，利用交叉偶联反应将 1,1,2,2-四氟乙基 (CF2CF2H) 基序掺入未活化的富电子烯基碘化物中。我们发现稳定的 Cu(CF2CF2H)(PPh2Me)3 复合物虽然不与这些底物发生反应，但可以作为有价值的 P 连接库，用于形成溶剂稳定的“无配体”和反应性 CuCF2CF2H 物质。添加 CuBr 后会发生这种转变，CuBr 会部分清除 CuBr(PPh2Me)3 形式的 P 配体。由此产生的原位生成的溶剂稳定的“无配体”系统显着增强了复合物的反应活性，特别是对于具有挑战性的富电子底物。这一进步使得 HCF2CF2-糖醛以及核苷/核碱基和芳烃的合成成为可能。