The creation of new chiral ligands capable of providing high stereocontrol in metal-catalyzed reactions is crucial in modern organic synthesis.The production of bioactive molecules as single enantiomers is increasingly required, and asymmetric catalysis with metal complexes constitutes one of the most efficient synthetic strategies to access optically active compounds.H erein we offer ah istorical overview on the development of chiral derivatives of the ubiquitous cyclopentadienyl ligand (Cp X ), and detail their successful application in abroad range of metal-catalyzed transformations.Those include the functionalization of challenging C À Hb onds and beyond, giving access to an extensive catalogue of valuable chiral molecules.Acritical comparison of the existing ligand families,their design, synthesis,and complexation to different metals is also provided. In addition, future researchdirections are discussed to further enhance the performance and application of Cp X ligands in enantioselective catalysis.

Mild complexations of chiral cyclopentadienes with rhodium(i) and iridium(i) precursors enable user-friendly in situ complex formation for catalytic applications.

Stable pre-ligands and common metal salts provide, via β-carbon elimination, access to Cp-metal complexes suitable for in situ catalyst preparation.