Catalysis of the Diels–Alder Reaction of Furan and Methyl Acrylate in Lewis Acidic Zeolites

Diels–Alder (DA) reactions of furans yield oxanorbornene derivatives which can be converted to a variety of molecules, ranging from molecules of biological interest to naturally occurring organic compounds, and to aromatics via dehydration, a promising alternative for the synthesis of aromatics from renewables. With furan being one of the less reactive dienes, the development of Lewis acidic heterogeneous catalysts, without the shortcomings of the traditional homogeneous catalysts, is critically important. Herein, we use computational chemistry to study the DA reaction of furan and methyl acrylate in three zeotypic Lewis acids, Sn-, Zr-, and Hf-BEA. We find that all three exhibit the same ability to enhance the electrophilic character of the dienophile and promote modest charge transfer from the diene. Despite being moderately Lewis acidic, they still achieve a reduction of about 12.5 kcal/mol in the activation energy relative to the reaction in the absence of catalyst.