In this Ph.D, the [3+X+3+X] (X= 5,6) reactivity of metal carbenes was extended to the synthesis of densely functionalized macrocycles which were synthesized using different cyclic ether precursors. The effect of substituents on the solid state conformation of these molecules was studied. Furthermore, a novel methodology was discovered which enabled not only the amidation of the ester groups but also a deconjugative transposition of C=C bonds. Chiral (racemic) macrocycles are then formed in a single step. Even if the two stereogenic centers are separated by more than 7 atoms, an excellent diastereoselectivity is achieved (dr >49:1). Different derivatives were used for an ion sensing study and for the synthesis of cryptands. An example of ditopic receptor is presented. Further applications in the field of supramolecular chemistry and catalysis are looked for.