Potential energy surface [Δ G (kcal mol -1 )] for the enantioselective nucleophilic desymmetrization of the P(V) compound P1 with 2-methyl-6-nitrophenol using the model BIMP catalyst B12-P(Ph) 3 computed at the SMD(fluorobenzene)/M06-2X/def2TZVP//SMD(fluorobenzene)/M06-2X/def2SVP level of theory. The reaction was found to proceed in three stages: complexation, nucleophilic attack and elimination from a metastable pentacoordinate intermediate. The rate- (and enantio-) determining step was found to be nucleophilic addition of the phenol to P1 with the TS leading to the ( R )-product ( TS1-( R ) ) being more favourable than that leading to the ( S )-product ( TS1-( S ) ) by 2.4 kcal mol -1 . Gibbs free energies (kcal mol -1 ) are reported in parenthesis. ArOH, 2-methyl-6-nitrophenol; Ar'OH, 2,4-dimethylphenol; SM, starting material.
