A Complementary Approach to Aromatic Synthesis by Diels-Alder Reactivity Followed by Desaturative Photoredox, Cobalt and HAT Triple Catalysis.

Aromatic molecules are integral to every aspect of chemistry. In general, the preparation of these compounds is approached via the use of aromatic precursors that are progressively functionalized using reactivity like electrophilic/nucleophilic aromatic substitution. Derivatives equipped with electron withdrawing groups (ester, ketone...) are particularly used in synthesis but are often challenge to prepare. This is because aromatic chemistry has to follow some stringent selectivity rules that activate or deactivate specific positions. This means that installing a functionality on a deactivated position (e.g. meta in an electron rich aromatic) is very difficult and requires many steps.This project seeks to address this challenge by developing an innovative approach to aromatic synthesis using simple Diels-Alder cycloadditions to construct a six-carbon cyclic framework followed by an unprecedented desaturation process. In particular, we will demonstrate the integration of three catalytic modes, photoredox + cobalt + HAT catalysis, as blueprint to progressively desaturate Diels-Alder cycloadduct to poly-functionliased aromatics. This reactivity will streamline the preparation of many high-value but difficult to make aromatic products, will be used in late-stage functionalizations and will substantially expand the fields of dual photoredoxcobalt catalysis and boryl radical chemistry.This research capitalizes on recent developments of the Leonori group that has experience in the development of methodologies based on both desaturation and boryl radical reactivity. The completion of such an innovative and ambitious project at RWTH Aachen University will be facilitated by generating, transferring, sharing and disseminating knowledge, and will enhance my future career following the training plan envisioned.