Having explored the scope with respect to the phenol nucleophiles, the scope of the P(V) electrophile was then assessed (Scheme 2, B). Electron donating (21-22) and electron withdrawing (23) substituents on the aromatic group were well tolerated with the desired products being obtained in 63-77% yield and >95:5 e.r. When a very electron poor aromatic group was introduced (24), however, lower temperature (-20 °C) and a 72 h reaction time was required to obtain the desired product in appreciable yield and 86:14 e.r. On the other hand, when a thiophene substituted electrophile was employed, the desired product 25 was obtained in 90% yield and 95:5 e.r. Subsequently, P(V) electrophiles bearing alkyl substituents were submitted to the optimized desymmetrization conditions. Methyl, ethyl, and n-hexyl derived substrates were all competent electrophiles in the desymmetrization with the desired products (26-28) being obtained in 88-97% yields and 90:10-93:7 e.r. Interestingly even more sterically demanding substituents on P, such as iso-propyl, could also be accommodated with the resulting enantioenriched product (29) being obtained in 79% yield and 94:6 e.r. This result is in stark contrast to the 7% yield and 77:23 e.r. obtained under the first-generation conditions, which most likely resulted from the steric repulsion arising between the hindered ortho-substituted phenol nucleophile and an encumbered electrophile. Use of a substrate bearing a chloromethyl substituent afforded the corresponding desymmetrised product 30 in 49% yield and 89:11 e.r., a result of diminished reactivity as opposed to the formation of side products. A phenylethyl-derived substrate was also well-tolerated, forming desymmetrised product 31 in 69% yield and 94:6 e.r. Benzylic substrates were also compatible with 32 being obtained in 65% yield and 91:9 e.r.