Bornemann Dustin, Pitts Cody Ross, Wettstein Lionel, Brüning Fabian, Küng Sebastian, Guan Liangyu, Trapp Nils, Grützmacher Hansjörg, Togni Antonio
Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 2, 8093, Zürich, Switzerland.
The Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, CA, USA.
Angew Chem Int Ed Engl. 2020 Dec 7;59(50):22790-22795. doi: 10.1002/anie.202010943. Epub 2020 Oct 2.
Fluorinated organophosphorus(V) compounds are a very versatile class of compounds, but the synthetic methods available to make them bear the disadvantages of 1) occasional handling of toxic or pyrophoric P starting materials and 2) a dependence on hazardous fluorinating reagents such as XeF . Herein, we present a simple solution and introduce a deoxygenative fluorination (DOF) approach that utilizes easy-to-handle phosphine oxides as starting materials and effectively replaces harsh fluorinating reagents by a combination of oxalyl chloride and potassium fluoride. The reaction has proven to be general, as R PF , R PF , and RPF compounds (as well as various cations and anions derived from these) are accessible in good yields and on up to a multi-gram scale. DFT calculations were used to bolster our observations. Notably, the discovery of this new method led to a convenient synthesis of 1) new difluorophosphonium ions, 2) hexafluorophosphate salts, and 3) fluorinated antimony- and arsenic- compounds.
氟化有机磷（V）化合物是一类用途广泛的化合物，但现有的合成方法存在以下缺点：1）偶尔需要处理有毒或自燃的磷起始原料；2）依赖危险的氟化试剂，如XeF₂。在此，我们提出了一种简单的解决方案，并引入了一种脱氧氟化（DOF）方法，该方法使用易于处理的氧化膦作为起始原料，并通过草酰氯和氟化钾的组合有效地替代了苛刻的氟化试剂。事实证明，该反应具有通用性，因为R₃PF₂、R₂PF₃和RPF₄化合物（以及由这些化合物衍生的各种阳离子和阴离子）都可以以良好的产率获得，并且规模可达数克。密度泛函理论（DFT）计算用于支持我们的观察结果。值得注意的是，这种新方法的发现使得以下化合物的便捷合成成为可能：1）新型二氟鏻离子；2）六氟磷酸盐；3）氟化锑和砷化合物。
