Development and Application of Methods for Catalytic Asymmetric Synthesis of Planar-Chiral Metallocene Complexes

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As shown in various planar-chiral metallocenylphosphine ligands, transition-metal complexes with planar chirality are useful chiral templates and have been utilized in asymmetric synthesis as chiral catalysts and chiral reagents. In spite of their usefulness, catalytic asymmetric reactions of preparing such planar-chiral compounds have bee extremely rare. In this research project, we have succeeded to develop various novel protocols of catalytically preparing planar-chiral metallocene derivatives in high enantiomeric purity. The methods we have developed include kinetic resolution of racemic planar-chiral metallocenes as well as asymmetric desymmetrization of planar-prochiral phosphaferrocenes. We have also demonstrated that our methods can be applicable to kinetic resolution of planar-chiral (η^6-arene)chromium complexes, indicating potential versatility of the protocols.