Metal Catalysed electrophilic amination of non-activated substrates using triazolinedione-inspired nitrenoid reagents

01 November 2019 → 31 October 2023
Research Foundation - Flanders (FWO)
Research disciplines
  • Natural sciences
    • Organic chemical synthesis
electrophilic amination
Project description

Chemical reactions that introduce nitrogen atoms in simple organic substrates are key transformations in both bulk industrial processes as well as in fine chemical or lab scale organic synthesis, in particular in drug discovery. However, the direct introduction of nitrogen on less functionalised organic substrates is a challenging task. Classical methods are limited in scope and can require harsh reaction conditions. From a conceptual point of view, the most useful synthetic transformations for the synthesis of nitrogen-containing compounds, would be direct nitrogenation or hydroamination reactions of simple hydrocarbon substrates. Whereas the related and well-known direct oxygenation and hydroxylation reactions of hydrocarbons are very common processes, both in synthetic as well as in biosynthetic transformations, direct aminations of hydrocarbons are quite rare. More importantly perhaps, whereas electrophilic oxygen-based species that can activate C-H and C=C bonds are common reagents, the related electrophilic nitrogen-based species are rare and the known examples are typically much less reactive electrophiles. The aim of this project is to investigate the use of azodicarboxylderivatives (both cyclic and linear versions) for the introduction of nitrogen in simple substrates via catalytic activation of their inherent carbene-like reactivity. Although azodicarboxyls are known as ligands in organometallic complexes, their reactivity has so far been little explored.