Table 1.
Relative energies of adducts for conversion of Sp, 1, to Gh, 7.
| Summary of Energetics | Schemes 2-4 Structure No. | E + ZPE + ΔH298 + ΔGsolv (kcal/mol) |
|---|---|---|
| Sp + CH+ + 3 H2O + CH3S- | 1 | 0.0 |
| Sp-N1Htaut + CH+ + 3 H2O + CH3S- | 1-N1H taut | 3.9 |
| Sp-N1HN3H imine + CH+ + 3 H2O + CH3S- | 1-N1HN3H imine | 1.9 |
| Sp-TS-Sp diol + CH+ + 1 H2O + CH3S- | 1/8 TS | 43.0 |
| Sp-TS-carbamate N3H enol + CH+ + 1 H2O + CH3S- | 1/14 TS | 51.2 |
| Sp-TS-isocyanate enol + CH+ + 1 H2O + CH3S- | 1/16 TS | 33.1 |
| Sp-C5OH+ + C + 3 H2O + CH3S- | 2-C5OH taut | 27.5 |
| Sp-N1H+ + C + 3 H2O + CH3S- | 2 | 4.1 |
| Sp-C6OH+ + C + 3 H2O + CH3S- | 2-C6OH taut | 17.9 |
| Sp-C6OH+ TS Sp diol N1H+ + C + 2 H2O + CH3S- | 2-C6OHtaut /3 TS | 43.1 |
| Sp-N1H+ TS carbamate enol N1H+ + C + 1 H2O + CH3S- | 2N1H+/14N1H+ TS | 38.1 |
| Sp-N1HH+TS-Sp diol-N1H+ + C + 1 H2O + CH3S- | 2/3 TS | 18.6 |
| Sp diol-N1H+ + C + 2 H2O + CH3S- | 3 | 11.8 |
| Sp diol-N1H+-TS-imidazolidine C4 carboxylic acid-N1H+ + C + 1 H2O + CH3S- | 3/4 TS | 46.9 |
| Sp diol-N1H+-(ring opening) TS-imidazolidine C4 carboxylic acid-C6OH+ + C + 2 H2O + CH3S- | 3/4C6OH+ TS | 48.9 |
| C4-carboxy-Gh N1H+ + C + 2 H2O + CH3S- | 4 | 12.8 |
| C4-carboxy-Gh N1H+ TS Gh enol cation + C + 2 H2O + CH3S- | 4/5TS | 35.7 |
| C4-carboxy-Gh C5OH+ + C + 2 H2O + CH3S- | 4C5OH+ TS | 42.3 |
| Gh enol N1H+ + C + 2 H2O + CH3S- + CO2 | 5 | 11.2 |
| Gh enol N1H+-TS-Gh keto N1H+ + C + CH3S- + CO2 | 5/6 TS | 35.5 |
| Gh keto N1H+ + C + 2 H2O + CH3S- + CO2 | 6 | -11.2 |
| Gh + CH+ + 2 H2O + CH3S- + CO2 | 7 | -5.5 |
| Sp diol + CH+ + 2 H2O + CH3S- | 8 | 14.7 |
| Sp diol-TS-C4-carboxy-Gh + CH+ + 2 H2O + CH3S- | 8/9 TS | 31.0 |
| C4-carboxy-Gh + CH+ + 2 H2O + CH3S- | 9 | 14.5 |
| C4-carboxy-Gh-TS-Gh enol + CH+ + CH3S- | 9/10 TS | 37.6 |
| Gh enol + CH+ + 2 H2O + CH3S- + CO2 | 10 | 19.1 |
| Gh enol-TS-Gh + CH+ + CH3S- + CO2 | 10/7 TS | 45.2 |
| SpC6diol anion + CH+ + 2 H2O + CH3SH | 11 | 21.8 |
| SpC6diol anion TS Gh anion + CH+ + 1 H2O + CH3SH | 11/13 TS | 47.4 |
| C4-carboxy-Gh anion + CH+ + 2 H2O + CH3SH | 12 | -2.0 |
| C4-carboxy-Gh anion-TS-Gh anion + CH+ + 2 H2O + CH3SH | 12/13 TS | 27.5 |
| Gh enol anion + CH+ + 2 H2O + CH3S- + CO2 | 13 | 17.7 |
| Carbamate N3H enol + CH+ + 2 H2O + CH3S- | 14 | 22.9 |
| Carbamate N3H enol-TS-Gh N3H enol + CH+ + 2 H2O + CH3S- | 14/10 TS | 38.4 |
| Carbamate N3H enol/keto + CH+ + CH3S- | 14/15 TS | 50.5 |
| Carbamate N1HN3H enol cation + C + 2 H2O + CH3S- | 14N1H+ | 24.0 |
| Carbamate N3H ketone + CH+ + 2 H2O + CH3S- | 15 | -8.5 |
| Carbamate N3H ketone-TS-Gh + CH+ + 1 H2O + CH3S- | 15/7 TS | 5.8 |
| Isocyanate enol + CH+ + 3 H2O + CH3S- | 16 | 33.9 |
| Isocyanate enol-TS-carbamate N1H enol + CH+ + 1 H2O + CH3S- | 16/17 TS | 63.4 |
| Isocyanate enol-keto tautomerization + CH+ + 1 H2O + CH3S- | 16/19 TS | 68.9 |
| Imidazolidone carbamate N1H enol + CH+ + 2 H2O + CH3S- | 17 | 24.5 |
| Imidazolidone carbamate N1H enol-TS-Gh enol + CH+ + 1 H2O + CH3S- | 17/18 TS | 55.7 |
| Gh enol + CH+ + 2 H2O + CH3S- + CO2 | 18 | 20.4 |
| Gh-enol-ketone TS + CH+ + CH3S- + CO2 | 18/21 TS | 47.0 |
| Isocyanate ketone + CH+ + 3 H2O + CH3S- | 19 | 22.9 |
| Isocyanate keto-TS-carbamate N1H keto + CH+ + 1 H2O + CH3S- | 19/20 TS | 46.5 |
| Imidazolidone carbamate N1H ketone + CH+ + 2 H2O + CH3S- | 20 | 1.4 |
| Imidazolidone carbamate N1H ketone-TS-Gh taut + CH+ + H2O + CH3S- | 20/21 TS | 31.1 |
| Gh N1H2 taut + CH+ + 2 H2O + CH3S- + CO2 | 21 | -2.9 |
| Gh N1H2 taut-TS-Gh + CH+ + H2O + CH3S- + CO2 | 21/7 TS | 13.1 |