Results for the bimolecular Houk–List–Tang–Wu mechanism in cyclohexanone and DMSO (values in brackets) computed using the B3LYP-D3/6-31G(d,p) method. The first two columns show the product final stereochemistry and encounters labels, as in Fig. 2. ΔE# and ΔG# labels the transition state energies and free energies with respect to the pre-reaction complex; ΔGCMPX labels the stabilization energy of the pre-reaction complexes; ΔGR the free energy differences between the product complex and the pre-reaction complex. rC–C and rO–H are the C–C and O–H lengths at the transition state in cyclohexanone (DMSO). Energies are in kcal mol−1.
| Stereoisomer | Encounter | ΔGCMPX | ΔG# | ΔGR | r c–c | r O–H |
|---|---|---|---|---|---|---|
| (S,R) | Re–Re (A)-anti | −12.87 (−13.00) | 10.41 (10.12) | 10.36 (9.98) | 1.90 (1.89) | 1.70 (1.70) |
| (S,S) | Re–Si (B)-syn | −13.33 (−13.66) | 13.29 (15.79) | 13.57 (12.56) | 1.81 (1.80) | 1.73 (1.73) |
| (R,S) | Si–Si-HL (C)-anti | −11.79 (−12.27) | 13.03 (12.92) | 11.75 (9.30) | 1.93 (1.92) | 1.68 (1.68) |
| (R,R) | Si–Re-HL (D)-syn | −11.04 (−11.34) | 16.52 (16.37) | 14.33 (13.61) | 1.96 (1.96) | 1.75 (1.75) |