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

本项目将开发一种新的催化和原子经济的均裂芳香取代反应，该反应基于质子耦合电子转移（PCET）作为重排和催化剂再生的关键步骤。PCET是许多生物催化体系和能量转换的关键步骤，但很少用于催化有机合成。我们希望利用这种巨大的潜力，在单电子步骤，而不是在两个电子步骤进行的经典方法进行催化。合成（Gansäuer，有机合成和催化剂合成）和机理组（Flowers，计算和动力学研究）之间的密切合作将允许识别对整个过程效率至关重要的因素。以这种方式，可以通过计算、动力学和合成研究之间的反馈回路来合理设计高效且稳定的催化剂的性质。待开发的反应与制备许多具有潜在高生物活性的化合物有关，例如α-芳基丙酸和具有缺电子芳烃的化合物，这些化合物不容易通过经典的亲电芳族取代获得。

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.