Sustainable Catalytic Synthesis of Diethyl Carbonate

Abstract New sustainable approaches should be developed to overcome equilibrium limitation of dialkyl carbonate synthesis from CO 2 and alcohols. Using tetraethyl orthosilicate (TEOS) and CO 2 with Zr catalysts, we report the first example of sustainable catalytic synthesis of diethyl carbonate (DEC). The disiloxane byproduct can be reverted to TEOS. Under the same conditions, DEC can be synthesized using a wide range of alkoxysilane substrates by investigating the effects of the number of ethoxy substituent in alkoxysilane substrates, alkyl chain, and unsaturated moiety on the fundamental property of this reaction. Mechanistic insights obtained by kinetic studies, labeling experiments, and spectroscopic investigations reveal that DEC is generated via nucleophilic ethoxylation of a CO 2 ‐inserted Zr catalyst and catalyst regeneration by TEOS. The unprecedented transformation offers a new approach toward a cleaner route for DEC synthesis using recyclable alkoxysilane.