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.

Vicinal diamines constitute one the most important functional motif in organic chemistry because of its wide occurrence in a variety of biological and pharmaceutical molecules. We report an efficient metal‐free, highly stereoselective intramolecular diamination using a novel chiral hypervalent iodine reagent together with its application as an efficient catalyst for the synthesis of diamines.

Figure 5. An overview of the current families of Cp X ligands.

Despite advances in the synthesis of polysubstituted cyclopentadienyl metal complexes, the rapid access to a library of monosubstituted Cp bearing metal complexes remains challenging. A convenient and general method to access a broad range of monosubstituted cyclopentadienyl rhodium­(I) and iridium­(I) complexes is reported. The process involves a direct nucleo-metalation of fulvenes with widely available metal precursors, affording a set of CpRhI(olefin)2 and CpIrI(olefin)2 complexes in high yields. A broad range of oxygen-, nitrogen-, and carbon-based nucleophiles were found competent for the process and offer good tuning abilities of the cyclopentadienyl portion.

A method for the catalytic, enantioselective, carbosulfenylation of alkenes to construct 3,4-disubstituted chromans is described. Alkene activation proceeds through the intermediacy of enantioenriched, configurationally stable thiiranium ions generated from catalytic, Lewis base activation of an electrophilic sulfenylating agent. The transformation affords difficult-to-generate, enantioenriched, 3,4-disubstituted chromans in moderate to high yields and excellent enantioselectivities. A variety of substituents are compatible including electronically diverse functional groups as well as several functional handles such as aryl halides, esters, anilines, and phenols. The resulting thioether moiety is amenable to a number of functional group manipulations and transformations. Notably, the pendant sulfide was successfully cleaved to furnish a free thiol which readily provides access to most sulfur-containing functional groups which are present in natural products and pharmaceuticals.