Alkali metal alkoxides play a pivotal role in nucleophilic alkoxylation reactions, offering pathways for the synthesis of ethers, including the increasingly sought-after trifluoromethyl ethers. However, the synthesis of long-chain perfluoroalkyl ethers remains a substantial challenge in this field. Through the innovative use of triglyme to encapsulate potassium ions, we enhanced the stability of short-lived, longer-chain perfluoroalkoxy anions, thereby facilitating efficient nucleophilic perfluoroalkoxylation reactions. This method provides a new precedent for the halo-perfluoroalkoxylation of gem-difluoroalkenes and offers a versatile tool for the design of perfluoroalkyl ethers, including those containing complex moieties of heterocycles and drug molecules. We also demonstrated the utility of the resulting halo-perfluoroalkoxyl adducts through various chemical transformations to valuable diverse perfluoroalkyl ethers.

中文翻译：

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三甘醇二甲醚中短寿命碱金属全氟醇盐对偕二氟烯烃的卤代全氟烷氧基化


碱金属醇盐在亲核烷氧基化反应中发挥着关键作用，为醚的合成提供了途径，包括日益抢手的三氟甲基醚。然而，长链全氟烷基醚的合成仍然是该领域的重大挑战。通过创新地使用三甘醇二甲醚封装钾离子，我们增强了短寿命、长链全氟烷氧基阴离子的稳定性，从而促进高效的亲核全氟烷氧基化反应。该方法为偕二氟烯烃的卤代全氟烷氧基化提供了新的先例，并为全氟烷基醚的设计提供了通用工具，包括那些含有杂环和药物分子复杂部分的全氟烷基醚。我们还证明了所得卤代全氟烷氧基加合物通过各种化学转化成有价值的各种全氟烷基醚的效用。