Facial Selectivity in Epoxidation of 2-Cyclohexen-1-ol with Peroxy Acids. A Computational DFT Study

We addressed the mechanism of epoxidation of 2-cyclohexen-1-ol by locating all the transition structures (TSs) for the reaction of peroxyformic acid (PFA) with both pseudoequatorial and pseudoaxial cyclohexenol conformers (five TSs for each conformer) and, for purpose of comparison, also those for the PFA epoxidation of cyclohexene. Geometry optimizations were performed at the B3LYP/6-31G* level, energies refined with single point B3LYP/6-311+G**// B3LYP/6-31G* calculations and solvent effects introduced with the CPCM method.