A highly diastereo- and enantioselective Pd(II)-catalyzed hydrophosphination of dienones with Ph(2)PH involving formation of double C*-P bonds has been developed, providing a series of chiral tertiary diphosphines (chiral PCP pincer ligands) in high yields. A catalytic cycle for the reaction was proposed.

A highly reactive, chemo- and enantioselective addition of diphenylphosphine to α,β-unsaturated imines catalyzed by a palladacycle has been developed, thus providing the access to a series of chiral tertiary enaminophosphines in high yields. A putative catalytic cycle has also been proposed.

A palladacycle-catalyzed diastereo-and enantioselective stepwise double hydrophosphination of bis(enones) with PhPH 2 has been developed, allowing intermolecular construction of chiral tertiary bulky P-heterocycles in one pot in high yields. A catalytic cycle for the reaction is proposed as well.

Our journey in organophosphorus research over the past 26 years is compiled in this Personal Account. Advances in palladacycle design have engendered a shift in our focus from template-mediated transformations to catalysis for the direct preparation of chiral phosphines containing a wide variety of functional groups. Novel approaches to access previously inaccessible phosphines and their applications in cancer research are summarized herein.

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