Chiral cyclopentadienyl (Cpx) metal complexes have empowered the developement of challenging asymmetric C(sp2)-H activation transformations. However the preparation of competent atropchiral Cpx ligands is long and tedious. Moreover the range of application of chiral Cpx catalysts in asymmetric C-H functionalization is limited to aryl C-H bonds. This thesis presents the elaboration of a library of atropchiral Cpx group-9 metal complexes via concise syntheses. Structural data were systematically collected and a rational analysis highlighted the flexibility of Cpx ligand to adapt to the steric environment of the metal center. Newly synthesized chiral rhodium Cpx complexes were competent in benchmark asymmetric C-H activation/allylation of arenes. Additionally, a fine tuning of chiral Cpx catalysts enabled a controled chemoselectivity in the asymmetric functionalization of alkenyl C-H bonds. A set of N-enoxysuccinimides and alkenes engaged selectively in the enantioselective Rh(III)-catalyzed cyclopropanation or carboamination of olefins in mild conditions. Mannitol-derived Cpx rhodium catalyst yielded cyclopropanes in high enantioselectivities while a tailored Binol-derived CpxRh(III) catalyst afforded amino esters with excellent enantioselectivities. The methods were applied in the synthesis of valuable amino acids derivatives and biologically active molecules.