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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 CO 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 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. 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.