Heterometallic Catalysts for Hydroamination Processes

The addition of amines to unsaturated hydrocarbons is a waste-free and atom-economic way to form nitrogen-containing compounds. This key technology enables the production of central bulk and fine chemicals as well as important pharmaceuticals from readily available amines and ubiquitous olefins and alkynes. Due to the high activation barrier the hydroamination reaction requires the presence of a catalyst. Despite the use of catalysts, industrial hydroamination processes are still very energy- intensive and require high temperatures and pressures and, furthermore, they suffer from poor conversion rates. The intermolecular hydroamination of unactivated amines and olefins is particularly challenging, still the corresponding products are of high importance to the chemical industry as building-blocks for more complex chemicals. Although catalysts for the intramolecular hydroamination/cyclisation have been developed for unactivated substrates, catalysts that perform similar intermolecular hydroamination are still rare and exhibit only very low activities. Therefore the development of hydroamination catalysts that readily convert unactivated substrates under energy- efficient conditions is highly sought-after. The state-of-the-art hydroamination catalysts work through activation of either the amine or the unsaturated hydrocarbon. For this project I will adapt an approach encountered in natural catalysts, enzymes, which often cope with challenging chemical reactions by cooperative substrate activation. I will combine both methods and develop heterometallic catalysts that simultaneously activate both the amine and the olefin in proximity to facilitate the hydroamination reaction. I aim to bind the different substrates in the catalyst next to each other thus mimicking an intramolecular hydroamination process and at the same time increase the reactivity of the substrates by individual activation. In this way I aim to solve the problem regarding intermolecular hydroamination of unactivated amines and olefins and exceed performance of state-of-the-art catalyst systems that rely on activation of either the amine or the unsaturated hydrocarbon. Furthermore, the use of bimetallic catalysts provides additional means to control the stereo- and regioselectivity during the hydroamination process. In the course of this project I aim to develop catalysts for the asymmetric, intermolecular hydroamination as well as for the very challenging anti-Markovnikov hydroamination of olefins. With this project I aim to contribute to the development of environmentally-benign and low-energy processes, especially hydroamination, for the cost-efficient production of industrially important base chemicals. Furthermore, it may act as a model system for the development of other catalytic applications including the broad range of hydrofunctionalisation processes.