Chiral organophosphorous compounds,including the C- and P-stereogenic phosphorous compounds,are of great significance in many fields such as the organic synthesis,asymmetric catalysis,biochemistry,pharmacy,and materials.However,conventional methods for preparation of these chiral organophosphorous compounds usually involve tedious procedures such as the multi-step resolution.Therefore,new efficient methods especially the catalytic transformations that can lead to chiral organophosphorous compounds in high enantio- or diastereo-selectivities are of high value and therefore highly desirable in the field.While further pursuing our transition-metal-mediated selective additions of P(O)-H compounds to carbon-carbon unsaturated compounds,1 we developed several efficient and practical methods for these useful chiral organophosphorous compounds,including a stereospecific nucleophilic substitution of optically pure H-phosphinates with organolithium or Grignard reagents that can lead to optically active secondary and tertiary phosphine oxides in high ee,a stereospecific coupling of P(O)-H compounds with amines or alcohols that can generate optically active organophosphorous acid derivatives,and transition-metal-catalyzed enantio- and diastereo-selective additions of P(O)-H compounds to carbon-carbon and carbon-oxygen unsaturated bonds.2