Direct Synthesis of Vinylene Carbonates from Aromatic Aldehydes**

Abstract Substituted vinylene carbonates were directly prepared from aromatic aldehydes following a one‐pot Benzoin condensation/transcarbonation sequence under solvent‐free conditions. The combination of a N ‐phenyl substituted triazolium salt NHC precursor and 4‐dimethylaminopyridine (DMAP) was found essential to reach high yield and selectivity. The reaction scope was investigated with a range of aromatic aldehydes and the corresponding vinylene carbonates were obtained with 32–86 % isolated yields (14 examples).