Amination of (Hetero)aryl Bromides via dual Copper-Photoredox Catalysis

发展温和而广泛适用的C(sp2) -N键形成方法是现代合成化学的核心挑战之一。在各种各样的药物、农用化学品和基本材料中出现的这些分子构建块说明了有机化学家对这种转化的根本兴趣。迄今为止，温和而有用的方法通常依赖于钯或镍催化剂的活化，而铜催化的变体通常受到主要限制。此外，与其他过渡金属催化剂相比，铜具有独特的性能，这使得铜催化反应方案的发展非常可取。本研究项目致力于开发一种普遍适用的方法，用于在（杂）芳基溴上结合氨基。潜在的策略是基于易于获得的，通常甚至是商业上可用的底物的应用，以及它们通过双铜光氧化还原催化的激活。目前普遍存在的铜催化C(sp2) -Br键活化的局限性预计将通过应用亲盐硅基自由基来克服。本文所述方案的成功开发将解决合成化学的一个未解决的问题，并将获得从容易获得的（杂）芳基溴开始的各种含C(sp2) - n的构建块的温和和直接的途径。此外，由于这一转变对其他研究领域的重要性，例如药物化学，有机合成的不同领域有望从这一进步中受益。

The development of mild and broadly applicable methods for the formation of C(sp2)‒N bonds is one of the central challenges of modern synthetic chemistry. The occurrence of these molecular building blocks in a wide variety of pharmaceuticals, agrochemicals, and basic materials illustrates the organic chemist’s fundamental interest in such a transformation. To date, mild and useful methodologies usually rely on the activation by palladium or nickel catalysts, while copper-catalyzed variants are generally restricted by major limitations. Additionally, copper features unique properties compared to other transition metal catalysts, and renders the development of a copper-catalyzed reaction protocol highly desirable.This research project is dedicated towards the development of a generally employable method for the incorporation of amino groups at (hetero)aryl bromides. The underlying strategy is based on the application of easily accessible and often even commercially available substrates, and their activation by dual copper-photoredox catalysis. Prevailing limitations of copper-catalyzed activations of C(sp2)‒Br bonds are envisioned to be overcome by the application of halophilic silyl radicals. The successful development of the protocol described herein would approach an unsolved issue of synthetic chemistry, and would gain mild and straightforward access to a variety of C(sp2)‒N-containing building blocks starting from easily accessible (hetero)aryl bromides. Furthermore, due to the importance of this transformation for other research fields, for example medicinal chemistry, different areas of organic synthesis are expected to benefit from this advancement.