Semistabilized Diazatrienyl Anions from Pyridine Imines and Acetylenes: An Access to ( Z )-Stilbene/Imidazopyridine Ensembles, Benzyl Imidazopyridines, and Beyond.

Semistabilized diazatrienyl anions are generated by the reaction of 2-pyridylarylimines with arylacetylenes in superbase systems MO t Bu (M = Li, Na, K)/DMSO at ambient temperature for 15 min. The initial intermediate N -centered propargyl-1,3-diaza-1,3,5-trienyl anions undergo intermolecular cyclization to benzyl imidazopyridine anions (formally [3 + 2] cycloaddition), further intercepting a second molecule of the starting pyridylimines or a proton of medium to afford ( Z )-stilbene/imidazopyridine ensembles and benzyl imidazopyridines. The charge distribution in all intermediate anions and their synthetic evolution are consistent with quantum-chemical analysis (B2PLYPD/6-311+G**//B3LYP/6-31+G*).