摘要
The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geometries of the reactants,transition states, intermediates and products were optimized at the B3LYP/6-31+G* level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-311+G* level was individually investigated. Polarizable continuum models(PCM)were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3,does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the ratelimiting step is reduced by 56.53 kJ mol-1 in gas and 44.84 kJ mol 1in solvent, demonstrating a high catalytic efficiency of CuI.
The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-（2-bromo-4-fluoro-phenyl）-l- cyclohexen-1-yl trifluoromethane-sulfonate was studied with the density functional theory （DFT）. The geometries of the reactants, transition states, intermediates and products were optimized at the B3LYP/6-31 ＋G＊ level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-31 I＋G＊ level was individually investigated. Polarizable continuum models （PCM） were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3, does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the rate- limiting step is reduced by 56.53 kJ mo1-1 in gas and 44.84 kJ mol-l in solvent, demonstrating a high catalytic efficiency of CuI.
