Development of Novel Desaturative Strategies for the Preparation of Aniline Building Blocks via Photoredox-Cobalt–HAT Triple Catalysis

Ziel

Anilines and their derivatives are integral organic molecules with application as medicines, agrochemicals and organic materials.

Over the last 30 years, the Buchwald-Hartwig and Ullmann cross-couplings have dominated the area of aromatic amination. These reactions involve palladium- or copper-catalyzed C-N bond formation between a halogenated aromatic and an amine. Only aromatics that have been halogenated will react with the metal catalysts and undergo cross-coupling. Therefore, although these processes are widely used, there are 2 significant challenges associated with them:

a. aromatic halogenation reactions are often problematic in terms of selectivity
b. cross-coupling reactions are known to fail on complex and functionalized materials

With this project we aim to provide a transformative advance in the field and demonstrate the direct conversion of functionalized N-cyclohexyl-amides, carbamates and sulfonamides into the corresponding N-aryl derivatives.

To achieve this, we will use an unprecedented triple catalysis manifold based on photoredox catalysis, cobalt catalysis and H-atom transfer catalysis. This innovative catalytic system will effectively trigger desaturation of the starting N-cyclohexyl derivatives and key reactive intermediates.

This research will create a novel approach for the one-step synthesis of many complex anilines from unusual precursors, which are largely commercially-available or easy to prepare.

The proposal capitalizes on recent developments by the host group in aniline synthesis and dual photoredox–cobalt catalysis.

The development of this innovative project at RWTH Aachen University will create new tools in bio-organic chemistry and enable the rapid and efficient preparation of high-value materials. Implementation of the project will be facilitated by the generation, transfer, and dissemination of knowledge, which will greatly enhance my future career prospects, in accordance with the enviosioned training plan.