Table 1. Addition of N-Methylaniline to Various Benzynesa.
| entry | 4a–e | computed ΔΔG⧧ (ratio 2:3) | experimental yield (ratio 2:3)b |
|---|---|---|---|
| 1a | 4a, X = OMe | 5.2 kcal/mol (>500:1) | 94% (2a formed exclusively) |
| 2 | 4b, X = F | 4.1 kcal/mol (>500:1) | 80% (2b formed exclusively) |
| 3 | 4c, X = Cl | 2.4 kcal/mol (>57:1) | 66% (>20:1) |
| 4 | 4d, X = Br | 1.4 kcal/mol (>11:1) | 67% (13:1) |
| 5 | 4e, X = I | 1.7 kcal/mol (>19:1) | 57% (9:1) |
a
Conditions: see Supporting Information. Computed ratios obtained from Boltzmann factors using B3LYP/6-31G(d) free energies including conductor-like polarizable continuum model (CPCM) solvation by MeCN.
b
Experimental yields and ratios are the average of three experiments and were determined by 1H NMR analysis using hexamethylbenzene as an external standard.