One-step catalytic synthesis of methyl acrylate from methyl acetate and trioxane, with 90.7% yield and 91.8% selectivity, was realized at 10-25 degrees 5. NMR analysis confirmed the ester enolization with generation of [i-Pr2EtN-H](+)[TfO](-) in the presence of i-Pr2EtN and Bu2BOTf, which was affected by solvent and base. The depolymerization of trioxane into formaldehyde was catalyzed by Bu2BOTf. The in-situ catalytic mechanism and efficiency of [i-Pr2EtN-H](+)[TfO](-) was determined and analyzed. Mechanism-based kinetic and thermodynamic studies were conducted for better understanding of this route. Also the primary process design and product separation simulation were carried out. (c) 2017 American Institute of Chemical Engineers AIChE J, 64: 1359-1372, 2018