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

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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.