Results for the trimolecular mechanism in cyclohexanone and DMSO (values in brackets) were computed using the B3LYP-D3/6-31G(d,p) method. The first two column show the product final stereochemistry and pro-chiral face arrangement. ΔE# labels the transition state energies; ΔECMPX label the stabilization energies of the pre-reaction complexes and ΔER the 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. Energies are in kcal mol−1.
| Product | Encounter | ΔECMPX | ΔE# | ΔER | r C–C [Å] | r O–H [Å] |
|---|---|---|---|---|---|---|
| (S,R) | (Re,Re)-5 | −18.17 (−23.25) | 1.77 (1.40) | −20.97 (−22.55) | 2.48 | 1.15 |
| (S,R) | (Re,Re)-6 | −26.50 (−30.81) | 4.49 (4.54) | −15.55 (−17.02) | 2.68 | 1.53 |
| (S,S) | (Re,Si)-5 | −21.88 (−27,42) | 2.51 (3.29) | −17.45 (−19.45) | 2.74 | 1.59 |
| (S,S) | (Re,Si)-6 | −18.81 (−21.70) | 2.29 (2.04) | −20.90 (−22.84) | 2.45 | 1.50 |
| (R,S) | (Si,Si)-5 | −23.68 (−27.94) | 8.52 (7.90) | −19.11 (−20.23) | 1.85 | 1.44 |
| (R,S) | (Si,Si)-6 | −22.50 (−24.63) | 19.30 (17.21) | −20.72 (−21.83) | 4.08 | 1.88 |
| (R,R) | (Si,Re)-5 | −20.87 (−24.63) | 3.07 (2.44) | −19.44 (−22.96) | 1.88 | 1.10 |
| (R,R) | (Si,Re)-6 | −22.89 (−26.08) | 6.28 (6.04) | −15.96 (−18.58) | 2.30 | 1.39 |