Stereoselective <i>C</i>(2)-Vinylation of 1-Substituted Imidazoles with 3-Phenyl-2-propynenitrile

First examples of direct vinylation of 1-substituted imidazoles at the 2-position of the imidazole nucleus are described. 1-Substituted imidazoles <b>1a−e</b> are <i>C</i>(2)-vinylated with 3-phenyl-2-propynenitrile (<b>2</b>) at room temperature without catalyst and solvent to afford 3-(1-organyl-1<i>H</i>-imidazol-2-yl)-3-phenyl-2-propenenitriles <b>3a−e</b>, mainly (<i>c.a.</i> 95%) as (<i>Z</i>)-isomers, in 56−88% yield. The reaction is likely to involve the zwitterionic intermediates, which prototropically isomerizes to imidazole carbene and eventually undergoes the selective 3,2-shift of the functionalized vinyl substituent.