Asymmetric synthesis and organometallic chemistry of functionalized phosphines containing stereogenic phosphorus centers

A series of organometallic reagents containing orthometalated chiral amine auxiliaries have been utilized as chiral templates to activate phospholes, vmylphosphines, and alkynylphosphines toward asymmetric ligand transformations via cycloaddition and hydroamination reactions. By a systemic manipulation of the subtle stereoelectronic properties of the auxiliaries and the metal centers, the template properties could be modified and the origins of stereoselectivity revealed. The chiral templates are able to control the disposition of selected functionalities into designated locations on the transformed P-stereogenic mono- and diphosphine ligands. This Account provides an overview of our recent work in this area.