In this communication, we disclose the first example of metal-free and site-selective radical fluorination of readily available tertiary alkyl ethers, enabled by synergistic photocatalysis and organocatalysis. This catalytic combination allows for exclusive fluorination of tertiary C-O bonds under mild conditions even in the presence of competing reaction sites. The excellent functional group tolerance affords valuable access to sterically hindered alkyl fluorides through late-stage modification of complex molecules. The successful use of tertiary alkyl ethers in radical fluorination enhances the structural diversity of aliphatic fluorides that can be derived from naturally abundant alcohols.

中文翻译：

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叔醚的可预测的位点选择性自由基氟化

在本交流中，我们公开了通过协同光催化和有机催化实现的，易于获得的叔烷基醚的无金属和位点选择性自由基氟化的第一个例子。这种催化组合允许在温和条件下，即使在存在竞争性反应位点的情况下，也可以对叔CO键进行独家氟化。出色的官能团耐受性可通过复杂分子的后期修饰提供有价值的位阻烷基氟化物。叔烷基醚在自由基氟化中的成功使用增强了可以衍生自天然丰富醇的脂肪族氟化物的结构多样性。