A more practical, general, and efficient second-generation enantioselective desymmetrization at P(V) has been developed. Through the use of thiazolidinone leaving groups on the P atom and fine tuning of the ureidopeptide BIMP catalyst numerous drawbacks of previously established methods have now been overcome. Phenols with a wide array of substitution patterns can be readily employed as nucleophiles in the desymmetrization step (vs. only ortho-substituted phenols previously) with both aryl and alkyl derived P(V) electrophiles as substrates. The remaining thiazolidinone leaving group can be readily displaced by medicinally relevant alkyl and aryl alcohols, amines, Grignard reagents and thiols, providing divergent access to a wide range of enantioenriched P(V) species through a single two-phase catalytic platform. In contrast to our first-generation approach the nucleophile employed for the desymmetrization could also be displaced enantiospecifically with either Grignard reagents to access tertiary phosphine oxides or with alkyl alcohols to access complex enantioenriched dialkyl phosphonates. DFT studies were then carried out to investigate the origins of enantioselectivity in the catalyst controlled desymmetrization step and to rationalize the superior enantioselectivities arising from the newly established pairing of the ureidopeptide BIMP catalyst and the thiazolidinone leaving group compared to the previously employed nitrophenol. Additionally, subsequent second and third stage enantiospecific nucleophilic substitutions progressing through either stereoinversive or retentive processes were also rationalized. Taken together, the newly developed catalytic platform, and computational insights obtained in this study provide a toolbox for the preparation and utilization of enantioenriched stereogenic at P(V) compounds as well as a road map for the development of even more general catalytic strategies to access this ever more important class of compound.