Synthetic approaches to enantiopure P(V) compounds can be subdivided into five categories (Scheme 1B). The first approach is classical resolution and/or separation of diastereomers or enantiomers by chromatography (Scheme 1B, i). A second approach revolves around the use of labile chiral auxiliaries which can be displaced by sequential diastereoselective nucleophilic additions to afford enantioenriched P(V) species (Scheme 1B, ii). Thirdly, chiral, yet racemic at P(V) electrophiles bearing a single leaving group (and often possessing a chiral sidechain) can be coupled diastereoselectively to enantiopure nucleophiles employing chiral catalysts (Scheme 1B, iii). A subsequent approach involves the direct functionalization of secondary phosphine oxides (SPO) by means of a metal catalyst bearing chiral ligands to obtain tertiary phosphine oxides. To date, however, this approach has been limited to the synthesis of all carbon substituted phosphine oxides (Scheme 1B, iv). The final strategy is an enantioselective desymmetrization by which prochiral groups linked to a phosphorus center are differentiated by a chiral catalyst (Scheme 1B, v). Multiple reactions have been developed using this strategy, however, until recently none have involved chemistry occurring at the P atom directly, but rather generate the P stereocenter indirectly (through manipulation of enantiotopic side chains) inherently limiting their scope. A strategically distinct enantioselective desymmetrization of P(V) species would involve an enantioselective nucleophilic substitution of enantiotopic leaving groups. By judicious choice of leaving group, nucleophile, and catalyst the desired enantioenriched species could be obtained in high yield and with excellent enantioselectivity (stage 1). The desymmetrized substrate would then still possess another leaving group, poised for a second (potentially enantiospecific) nucleophilic substitution reaction enabling diverse downstream derivatization opportunities (stage 2). This two-phase strategy would allow for a wide range of P(V) compounds to be accessed from a common intermediate, overcoming one of the main limitations of current enantioselective desymmetrization approaches (Scheme 1C).