Novel arene transformations through nucleophilic dearomatization

This PhD program will focus on designing conceptually new synthetically useful arene functionalisations through ring expansion reactions and C-X bond activation. The first approach will be based on the cleavage of the aromatic ring C-C bonds as a key step. This step is notoriously challenging as it could not be conducted selectively even with the most active transition metal complexes. Recently, we successfully addressed this problem by applying a novel concept of metal-induced ring strain with iridium complexes (Angew. Chem. Int. Ed. 2017, 56, 3266; J. Am. Chem. Soc., 2019, 141 , 6048). In this project, we will take one step further and explore an alternative strategy for the aromatic C-C cleavage that will not require the use of transition metals. This strategy will rely on a selective dearomatisation using stable difunctional nucleophilic reagents and designer Lewis acids as a central concept. It would address the limitations of known ring expansion methods based on the application of highly reactive and unselective carbenes and nitrenes. The second approach will focus on novel photochemical functionalisations of aromatic C-H and C-Hal bonds using well-defined transition metal complexes and sensitising additives.
During work on the project, the candidate will receive extensive training in organic and organometallic synthesis using Schlenk and glovebox techniques and will have hands-on experience in application of modern analytical methods (NMR, MS, GC/MS and HPLC). The knowledge and skills developed will provide the candidate with a solid foundation for his/her future academic or industrial career in organic chemistry and catalysis.