Geunes Eric P, Meinhardt Jonathan M, Wu Emily J, Knowles Robert R
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
J Am Chem Soc. 2023 Oct 11;145(40):21738-21744. doi: 10.1021/jacs.3c08428. Epub 2023 Oct 3.
We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and an excited-state iridium photocatalyst affords an aminium radical cation (ARC) intermediate that undergoes C-N bond formation with a nucleophilic alkene. Integral to reaction success is the electronic character of the amine, wherein increasingly electron-deficient heteroaryl amines generate increasingly reactive ARCs. Counteranion-dependent reactivity is observed, and iridium triflate photocatalysts are employed in place of conventional iridium hexafluorophosphate complexes. This method exhibits broad functional group tolerance across 55 examples of -alkylated products derived from pharmaceutically relevant heteroaryl amines.
我们报道了一种光驱动的方法，用于实现烯烃与伯杂芳基胺的分子间反马氏氢胺化反应。在该反应体系中，胺底物与激发态铱光催化剂之间发生电子转移，生成一个铵基自由基阳离子（ARC）中间体，该中间体与亲核烯烃发生C-N键形成反应。胺的电子性质是反应成功的关键，其中缺电子程度越高的杂芳基胺生成的ARC反应活性越高。观察到了反离子依赖性反应活性，使用三氟甲磺酸铱光催化剂代替传统的六氟磷酸铱配合物。该方法对55个源自药学相关杂芳基胺的N-烷基化产物实例表现出广泛的官能团耐受性。
