Funding

Currently, we are supported by National Science Centre, Poland, within Sonata grant (2020/39/D/ST4/01152) entitled ‘Controlling Regioselectivity of Catalytic Transfer Hydrofunctionalization Reactions by Non-covalent Interactions’.

Project description:

Transition metal catalysis provides new important tools for organic synthesis. The development of new strategies in this field enables the discovery of new synthetic protocols, improving existing processes, and saving costs, resources, and energy. Moreover, addressing general issues in catalysis, such as chemo- or regioselectivity of catalytic methodologies often streamlines their broad laboratory and further industrial applications.

In recent years, one of the revolutionary concepts, namely shuttle catalysis has been introduced and explored. This strategy enables the formal transfer of small molecules (e.g., HCN, H2/CO, HBr) between donor and (unsaturated) acceptor molecules and thus can be utilized as a powerful synthetic tool for the functionalization of unsaturated substrates. However, when unsymmetrical compounds (alkenes or alkynes) are used in such transformations, mixtures of regioisomers are formed, irrespective of type of transferred functional groups. This general limitation of shuttle hydrofunctionalization hampers the synthetic utility of the strategy, unless control of regioselectivity is achieved.

In this project, we hypothesize that the utilization of non-covalent interactions bears the potential to address the challenge of regioselectivity control in transfer hydrofunctionalization reactions. We postulate that new classes of precisely designed supramolecular catalysts (SupraCats) will selectively promote the formation of one target regioisomer. Such catalysts will exploit additional non-covalent interactions to preorganize a substrate at the transition metal center. Therefore, the main goal of the project is to explore non-covalent interactions controlling regioselectivity of catalytic transfer hydrofunctionalization reactions.

In contrast to previous supramolecular strategies that typically construct elaborated ligands from scratch, I propose to introduce supramolecular (recognition) units to the well described but unselective catalysts with modular approach. Utilization of different recognition units will enable a broad scope of prospective substrates. Therefore, the versatility of the approach, a feature usually non-accessible in so far investigated supramolecular catalytic systems, will be achieved.

Overall, the project will introduce a new, powerful approach to control the selectivity of transfer hydrofunctionalization reactions, while at the same time, building on recent advances in the field of supramolecular chemistry and catalysis. Consequently, this approach will provide access to a broad range of chemicals (e.g., nitriles, aldehydes, halides), the selective formation of which is currently limited but desired for both the development and production of fine-chemicals and materials.

These aspects have great potential of applicability in other fields: easier synthesis of pharmaceuticals, simplifying the production of materials, reducing side reactions and contaminants, access to new materials from available precursors, development of environmental-friendly and energy-efficient industrial processes.