Fluorine-containing organic molecules, particularly those that bear (sp³)C–F bonds, are rapidly gaining prominence in modern chemical synthesis. Although extensive studies have been devoted to the preparation of secondary and tertiary fluorides, crucial shortcomings remain: for example, lengthy substrate synthesis, contrived installation of difficult-to-remove directing/activating units, excessive waste generation and/or limited functional group compatibility. Here, we show that readily accessible α-monofluoro carboxylic acids, which are conventionally difficult substrates for cross-coupling, undergo direct decarboxylative cross-coupling with sp²- and sp³-hybridized organohalides to afford a wide assortment of fluorinated products. Reactions are typically promoted by a combination of 1 mol % of an Ir-based photocatalyst and 2–15 mol % of a bipyridine–Ni complex, delivering products in up to 86% yield under blue LED light irradiation. Concise synthesis of key therapeutic candidates underscores utility, complementarity, and distinct advantages compared with existing methods. DFT calculations are used to rationalize the distinct reactivity of α-fluoro carboxylic acid substrates (vs nonfluorinated parent acids) under decarboxylation conditions.

中文翻译：

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直接将α-氟羧酸参与脱羧CC键的形成

含氟有机分子，特别是带有（sp ³）C-F键的有机分子，在现代化学合成中迅速得到重视。尽管已经对仲和叔氟化物的制备进行了广泛的研究，但是仍然存在关键的缺点：例如，长时间的底物合成，难以去除的导向/活化单元的设计安装，过多的废物产生和/或官能团相容性有限。在这里，我们显示了易于获得的α-一氟羧酸，它们通常是交叉偶联的困难底物，与sp ^2-和sp ³进行直接脱羧交叉偶联。-杂交有机卤化物，可提供各种各样的氟化产物。通常通过1 mol％的Ir基光催化剂和2-15 mol％的联吡啶-Ni络合物的组合来促进反应，从而在蓝色LED照射下以高达86％的产率提供产物。与现有方法相比，关键治疗候选物的简明合成突出了实用性，互补性和独特的优势。DFT计算用于合理化脱羧条件下α-氟代羧酸底物（相对于非氟化母体酸）的独特反应性。