There is a perpetual need for efficient and mild methods to integrate deuterium atoms into carbon frameworks through late-stage modifications. We have developed a simple and highly effective synthetic route for hydrogen isotope exchange (HIE) in aromatic compounds under ambient conditions. This method utilizes catalytic amounts of hexafluorophosphate (PF6−) in deuterated 1,1,1,3,3,3-hexafluoroisopropanol (HFIP-d1) and D2O. Phenols, anilines, anisoles, and heterocyclic compounds were converted with high yields and excellent deuterium incorporations, which allows for the synthesis of a wide range of deuterated aromatic compounds. Spectroscopic and theoretical studies show that an interactive H-bonding network triggered by HFIP-d1 activates the typically inert P-F bond in PF6- for D2O addition. The thus in-situ formed DPO2F2 triggers then HIE, offering a new way to deuterated building blocks, drugs, and natural-product derivatives with high deuterium incorporation via the activation of strong bonds.

中文翻译：

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氟化环境中六氟磷酸盐触发的氢同位素交换 （HIE）：通过强键活化对芳香族化合物进行氘化的平台


永远需要一种高效和温和的方法，通过后期改性将氘原子整合到碳框架中。我们开发了一种简单且高效的合成路线，用于在环境条件下芳香族化合物中进行氢同位素交换 （HIE）。该方法利用氘代 1,1,1,3,3,3-六氟异丙醇 （HFIP-d1） 和 D2O 中的催化量的六氟磷酸盐 （PF6−）。酚类、苯胺类、苯甲醚和杂环化合物以高产率和出色的氘掺入率进行转化，从而可以合成多种氘代芳香族化合物。光谱和理论研究表明，由 HFIP-d1 触发的交互式 H 键网络激活了 PF6- 中通常惰性的 P-F 键，以进行 D2O 添加。这样原位形成的 DPO2F2 触发然后是 HIE，通过激活强键为氘化构建单元、药物和具有高氘掺入的天然产物衍生物提供了一种新方法。