Multi-substituted benzene is a ubiquitous and important structural unit found in various natural products, advanced functional materials and ligands of organometallic compounds. Among the various types of multi-substituted benzenes, the 1,3,5-trisubstituted ones are of great importance for their diverse applications in material science.Recently, The researchers in LMRF developed an oxidative NHC-catalyzed [2+4] annulation of enals and α-cyano-β-methylenones for the synthesis of multi-substituted benzenes through the cascade reaction of the dienolate and unsaturatedacyl azolium. Based on their work, they further reported that the NHC-catalyzed annulation of bromoenals and α-cyano-β-methylenones could give the corresponding cyanocyclohexadiene with Cs₂CO₃ as the base, which can be transformed into the 1,3,5-trisubstituted benzenes in the presence of DBU.

 Adv. Synth. Catal. 2016, 358, 2862. (VIP) , Org. Lett. 2016, 18, 6408.