Assessment of reactivities with explicit and implicit solvent models: QM/MM and gas-phase evaluation of three different Ag-catalysed furan ring formation routes

摘要: QM/MM molecular dynamics and static DFT calculations have been performed to evaluate free energy barriers reaction energies of a representative silver-catalyzed in DMF. The mechanism developed previous work revealed favorable intramolecular C–O coupling between terminal alkyne β-ketoester moieties yield furan ring three possible pathways were scrutinized within the framework SMD implicit solvation model. In this study we set out compare effect explicit on variations ring-closure step. feature different charge states with bonding topologies characteristic many silver- copper-catalyzed steps; hence they can serve as blueprint for assessing effects solvents wider reactions. Comparison results showed that both methodologies could unequivocally determine most well least likely pathway. Further analysis trajectories obtained from simulations indicated neither direct solvent participation nor any site-specific interaction reactant despite fact pairwise interactions solutes highly polar molecules are significant. These insights point sufficiently mobile, fluctuating shell which be efficiently substituted by models at fraction computational costs.