Aminophosphonic derivates are an important class of biologically active molecules. In this research, we consider phosphonoazadienes as valuable building blocks for the synthesis of such compounds. Phosphonoazadienes form a particular class of ambivalent reagents (electrophiles/dienes). A profound understanding of their behaviour (computational chemistry) will guide us in the synthesis of new tunable phosphonoazadienes, opening the way to new 1-phosphono azaheterocycles.