Jacobsen offered an elegant and complementary approach employing phosphoryl dichlorides (Scheme 1, D2). Under thiourea catalysis, the Jacobsen group was able to displace one of the enantiotopic chlorine atoms with specific amine nucleophiles, then, in the same pot a second enantiospecific substitution could take place using a large excess of alkoxide, phenoxide, thiolate or organomagnesium nucleophiles, with both steps taking place under high dilution and at cryogenic temperatures. Notably, only aryl substituted phosphoryl dichlorides were competent substrates for this transformation, while alkyl substituted phosphoryl dichlorides were inefficient substrates under the optimized conditions. The amine substituent of the phosphorus stereocenter could then be displaced enantiospecifically with solvent quantities of simple alkyl alcohols (MeOH, EtOH, allyl alcohol) under Brønsted acidic conditions. Only after this second, enantiospecific step, the resulting enantioenriched P(V) product could be further functionalized enantiospecifically with a variety of nucleophiles depending on the nucleophile previously used to displace the second chloride substituent. For example, if phenyl thiolate was employed, it could be replaced by more complex alkyl alcohols, if para-CF3-phenoxide was used, it could then be replaced by a Grignard reagent.