International Collaboration in Chemistry: Catalytic Atom-Economical Aromatic Substitution via Radicals

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In this project, a new catalytic and atom economical homolytic aromatic substitution reaction will be developed that is based on proton coupled electron transfer (PCET) as the key step for rearomatization and catalyst regeneration. PCET is a key-step in many biological catalytic systems and energy conversion but has only rarely been employed in catalytic organic synthesis. We wish to tap this large potential for catalysis proceeding in single electron steps rather than classical methods proceeding in two electron steps. The close collaboration between the synthetic (Gansäuer, organic synthesis and catalyst synthesis) and mechanistic group (Flowers, computational and kinetic studies) will allow an identification of the factors critical for the efficiency of the overall process. In this manner, the properties of an efficient and stable catalyst can be rationally designed through a feed-back loop between computational, kinetic, and synthetic investigations. The reaction to be developed is of relevance for the preparation of a number of compounds with potentially high biological activity, such as α-aryl propionic acids and compounds with electron deficient arenes that are not readily obtained via classical electrophilic aromatic substitutions.