Three-component reaction of imidazoles, cyanophenylacetylene, and chalcogens: stereoselective synthesis of 3-alkenyl-2-imidazolethiones and -selones

The three-component reaction of 1-substituted imidazoles, cyanophenylacetylene, and elemental sulfur or selenium proceeds readily (for sulfur at room temperature without solvent, and for selenium in boiling MeCN) to stereoselectively afford 3-(Z)-cyanophenylethenyl-2-imidazolethiones or -selones in yields ranging 39–97% (for thiones) and 39–84% (for selones). In this reaction, tellurium is inactive both under the above conditions and upon heating (50–55 °C) in DMSO, instead, only the C(2)-vinylation of the imidazole ring in up to 98% yield takes place. The Z-stereoselectivity of the reaction is close to 100% (for sulfur) and reaches 91–99% (for selenium). The reaction involves the zwitterionic adduct of imidazoles with cyanophenylacetylene, which converts to the carbene via proton transfer (from the imidazole 2 position to the carbanionic site of the zwitterion) further reacting with chalcogens.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slide