The resulting enantioenriched intermediates could then be converted to an even greater range of distinct classes P(V) of compounds by displacement of the remaining leaving group as well as allowing for even further diversification downstream. Density functional theory (DFT) calculations were performed to pinpoint the origin of enantioselectivity for the BIMP-catalyzed desymmetrization, to rationalize how a superior catalyst/leaving group combination leads to increased generality in our second-generation catalytic system, as well as to shed light onto observed retention and inversion pathways when performing late-stage enantiospecific SN2@P reactions with Grignard reagents.