Esterification of Tertiary Amides by Alcohols Through C−N Bond Cleavage over CeO2

Abstract CeO 2 has been found to promote ester forming alcoholysis reactions of tertiary amides. The present catalytic system is operationally simple, recyclable, and it does not require additives. The esterification process displays a wide substrate scope (>45 examples; up to 93 % isolated yield). Results of a density functional theory (DFT) study combined with in situ FT‐IR observations indicate that the process proceeds through rate limiting addition of a CeO 2 lattice oxygen to the carbonyl group of the adsorbed acetamide species with energy barrier of 17.0 kcal/mol. This value matches well with experimental value (17.9 kcal/mol) obtained from analysis of the Arrhenius plot. Further studies by in situ FT‐IR and temperature programmed desorption using probe molecules demonstrate that both acidic and basic properties are important, and consequently, CeO 2 showed the best performance for the C−N bond cleavage reaction.