Our research line was focused on the development of the new methodologies for the synthesis of nitrogen-containing building blocks under metal-free conditions. These structural fragments exhibit clear biological properties and their importance is further extended to organic, medicinal and material chemistry.

We aimed to design the synthesis of new hypervalent iodine(III/I) compounds and study their reactivity towards aromatic hydrocarbons and heterocycles. The idea was to incorporate nitrogenated molecule into the coordination sphere of the hypervalent iodine reagent, thus allowing us to use only one molecule as oxidant, nitrogen source and hydrogen acceptor for the synthesis of protected anilines.

We started our journey with the screening of the suitable nitrogen sources. We utilized ability of the hypervalent iodine reagents to undergo ligand exchange events. Throughout investigation we discovered, that tetrafluoro phthalimide is the best candidate for the desired transformation.

The second goal was to synthesize the novel hypervalent iodine(III) species with the chosen nitrogen source and study its reactivity towards aromatic substrates. After a thorough investigation, we established a synthesis of the novel I(III) compound. This type of compounds believed to have an unstable nature, nonetheless we were able to isolate analytically pure crystals and confirmed its structure by X-Ray analysis.

Lastly, we aimed to contextualize the structure, chemistry, and reactivity of complex anionic halide reagents to apply it to current research. We complemented this field with the synthesis and complete characterization of the novel complex anionic halide reagent with tetrafluoro-phthalimide as ligands. Furthermore, we discovered its synthetic potential in the amination of the pyrrole substrate class. Historically, the oxidation of pyrroles has been perceived as unpredictable, too tricky, or low yielding to be synthetically useful. Nevertheless, we were able to obtain good yields of synthetically useful intermediates, particularly 2-aminopyrroles. The developed method uses mild reaction conditions. To the best of our knowledge, there are no methodologies known for the direct amination of the aromatic C-H bond in pyrrole.

Overall, this doctoral thesis demonstrates a high potential of the novel complex anionic halide reagents that can unlock reactivities not achievable through classical, well-established approaches.

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