3D: Show Hide Print
Calculated(a) transition state properties, B3LYP+GD3BJ/Def2-TZVPP/SCRF=ethanol
Uncatalyzed reaction, TSb
Ar ΔG‡trans νi, cm-1 C-C, Å C-O, Å FAIR data DOI
p-NH2 15.01 483 1.950 3.137 10.14469/hpc/4102
p-OMe 18.30 448 1.917 2.807 10.14469/hpc/4100
p-Me 20.47 447 1.915 2.660 10.14469/hpc/4137
p-Cl 18.51 447 1.914 2.576 10.14469/hpc/4098
p-H 21.22c 452 1.919 2.574 10.14469/hpc/4099
p-CN 21.30 450 1.915 2.482 10.14469/hpc/4103
p-NO2 21.34 447 1.915 2.464 10.14469/hpc/4101
HCl catalyzed reaction, TS1d
Ar ΔG‡transc νi, cm-1 C-C, Å C-O, Å Dipole, D ΔΔG‡cis-transd
p-NH2 4.03 312 2.082 2.297 17.91 +8.19
p-OMe 8.45 440 1.978 3.218 19.83 +8.05
p-Me 9.89 412 1.928 3.164 18.49 +8.59
p-Cl 12.28 372 1.884 3.060 19.05 +8.44
p-H 13.01 375 1.890 3.069 18.65 +7.03
p-CN 17.62 279 1.810 2.871 20.08 +5.80
p-NO2 18.24 238 1.788 2.793 18.70 +7.02
HCl catalyzed reaction, TS2
Ar ΔG‡transc νi, cm-1 Dipole, D ΔΔG‡cis-transe Trans
ΔΔGprod-reactd		 Cis
ΔΔGprod-reacte
p-NH2 6.36 243 10.66 -0.29 -0.19 -5.04
p-OMe 8.48 270 11.39 +1.11 -0.67 -4.87
p-Me 10.04 208 12.16 +1.64 -1.27 -5.20
p-H 11.51 82 12.98 f -0.19 -4.75
p-Cl 11.84 101 12.94 f -0.11 -4.47
p-CN 18.02 16 16.07 f +0.17 -3.94
p-NO2 19.85 17 16.34 f +0.95 -3.25
Highest ΔG‡ for HCl catalysed mechanismd
Ar ΔG‡trans rds
p-NH2 6.36 TS2
p-OMe 8.48 TS1≈TS2
p-Me 10.04 TS1≈TS2
p-Cl 12.28 TS1
p-H 13.01 TS1
p-CN 18.02 TS2
p-NO2 19.85 TS2
Computed NCI (non-covalent-interaction) isosurfaces
p-NH2 trans cis
aAll energies in kcal mol-1; DOI for overall collection containing full data, 10.14469/hpc/3943, bCollection for trans stereochemistry 10.14469/hpc/3984, cΔΔG‡ for cis stereochemistry +5.57 kcal/mol. dCollection for trans stereochemistry, 10.14469/hpc/3985, eCollection for cis stereochemistry, 10.14469/hpc/4068, fTS2 is not a stationary point for this substituent.