A second generation catalytic two-phase strategy for the enantioselective synthesis of chiral at P(V) compounds is described. This protocol, consisting of a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization of prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows for divergent access to a wide range of C-, N-, O-and S-substituted P(V) containing compounds from a handful of enantioenriched precursors. A new catalyst/leaving group combination allowed for a far wider substrate scope and increased reaction efficiency and practicality over previously established protocols.