N‐Heterocyclic Olefins as Robust Organocatalyst for the Chemical Conversion of Carbon Dioxide to Value‐Added Chemicals

Abstract In this report, the activity of N‐heterocyclic olefins (NHOs) as a newly emerging class of organocatalyst is investigated for the chemical fixation of carbon dioxide through reactions with aziridines to form oxazolidinones and the N ‐formylation of amines with polymethylhydrosiloxane (PMHS) or 9‐borabicyclo[3.3.1]nonane (9‐BBN) as the reducing agent under mild conditions. The exocyclic carbon atoms of NHOs are highly nucleophilic owing to the electron‐donating ability of the two nitrogen atoms. This high nucleophilicity of the NHOs activates CO 2 molecules to form zwitterionic NHO–carboxylate (NHO–CO 2 ) adducts, which are active in formylation reactions as well as the carboxylation of aziridines to oxazolidinones.