Polydentate ligands with nitrogen donor atoms have possibly given rise to the largest group of coordination complexes described. Among these ligands, amidinates represent a nitrogenated version of carboxylates and allow the formation of complexes with most elements in the periodic table, adopting chelate or bridge coordination modes. The precursors of these ligands, amidines, can present an alkynyl group as the substituent of their central atom, R'N=C(C≡CR)NHR', which provides an additional point of reactivity for these molecules, as well as a different electronic behavior compared to conventional amidines with alkyl groups on the central carbon atom of the amidine group. These propiolamidines have been obtained through classical stoichiometric organic synthesis procedures or, with greater atomic economy, through catalytic procedures based on Main Group, Transition, or Rare Earth metals. This work reviews these synthesis methods, as well as the reactivity in the obtention of new, more complex heterocyclic organic molecules.