Li Li, Rawal Viresh H
Department of Chemistry, University of Chicago, Chicago, Illinois 60637, United States.
Chem. 2024 Oct 10;10(10):3243-3253. doi: 10.1016/j.chempr.2024.07.036. Epub 2024 Sep 2.
Arylethylamines represent a privileged scaffold in pharmaceutical compounds and form the backbone of many medical drugs, including those used for treating neurological diseases and pain. Their biomedical significance has inspired new synthetic methods that rely on transition metal-catalyzed aminoarylation reaction to an alkene, often in conjunction with a photoredox catalyst or a photosensitizer, and guided by a directing or stabilizing group. Here, we introduce a simple and effective method for azidoarylation of unactivated alkenes under transition metal-free conditions. Visible or near-UV light irradiation of readily available triarylbismuth dichlorides generates an aryl radical that selectively adds to the alkene, and the resulting homobenzyl radical is intercepted by an amine equivalent. This method offers a broad substrate scope and also enables aryl chlorination and arylcyanation of unactivated alkenes.
芳基乙胺是药物化合物中的一种优势骨架，构成了许多药物的核心结构，包括用于治疗神经疾病和疼痛的药物。它们的生物医学重要性激发了新的合成方法，这些方法通常依赖于过渡金属催化的烯烃氨基芳基化反应，并常常与光氧化还原催化剂或光敏剂结合使用，且受导向或稳定基团的引导。在此，我们介绍一种在无过渡金属条件下对未活化烯烃进行叠氮芳基化的简单有效方法。对易于获得的二氯三芳基铋进行可见光或近紫外光照射会产生一个芳基自由基，该自由基会选择性地加成到烯烃上，生成的亚苄基自由基会被胺当量捕获。该方法具有广泛的底物范围，还能实现未活化烯烃的芳基氯化和芳基氰化反应。
