Table 4. Distortion–Interaction and NBO Analysis for the Diastereomeric Transition States.
| ΔEdist_Aa | ΔEdist_Ba | ΔEd | ΔEi | ΔEactb | ΔH | ΔG | π(C=C)–σ*(S–Se)c | |
|---|---|---|---|---|---|---|---|---|
| TSRe-1 | 10.8 | 19.6 | 30.4 | –26.7 | 3.7 (0.0) | 4.5 (0.0) | 13.2 (0.0) | 76.7 (6.2) |
| TSRe-2 | 11.2 | 20.4 | 31.6 | –26.3 | 5.4 (1.7) | 6.2 (1.7) | 14.8 (1.6) | 70.5 (0.0) |
| TSSi-1 | 11.1 | 20.5 | 31.6 | –27.3 | 4.3 (0.6) | 5.3 (0.8) | 14.1 (0.9) | 76.8 (6.3) |
| TSSi-2 | 10.2 | 21.1 | 31.3 | –26.4 | 4.9 (1.2) | 5.7 (1.2) | 14.9 (1.7) | 71.7 (1.2) |
a
A = silyl enol ether (Z)-1a. B = catalytically active species (S)-VIII.
b
ΔEact = ΔEd + ΔEi (ΔEd = ΔEdist_A + ΔEdist_B).
c
π(C=C)−σ*(S–Se) orbital interaction energy is calculated by NBO analysis.