Nitrogen is a necessary element for life. This importance is represented in the composition of
developed medicines. The classic reactivity of nitrogen, as a nucleophile, needs to react it with an electrophile. This can prevent reactions with electron‑rich species. Electron-poor nitrogenated derivatives exist and are well-known in the literature.
In this thesis, the reactivity of electrophilic nitrogenated derivatives has been studied. First, the reactivity of chloramines has been explored with a nucleophilic trifluoromethylation reaction. In this study, chloramines showed a preferred attack on the chlorine atom. The complex [(phen)CuCF3] enabled the synthesis of N‑trifluoromethylated derivatives up to 100 % yield. Mechanistic studies could show DFT and experimental clues towards the radical nature
of the mechanism.
The transfer hydroamination has also been studied. An O-formylated oxime has allowed the
bifunctionalization of an insaturation with the nitrogen atom from the oxime and the hydrogen atom from the formyl group, with extrusion of CO2. This reaction also shows a radical nature. The catalytic system is a major challenge as the reaction produced 5 different compounds. A High-throuphut experiment enabled to observe the efficiency of many conditions. From a copper complex and a diphosphine ligand the formation of a pyrroline derivative has been oobserved at 100 °C in 18 h.
Keywords: chloramines, oximes, copper(I)