We report here an alternative and tunable metal-free synthesis of benzo[b]chalcogenophenes via the electrophilic cyclization of 2-functionalized chalcogenoalkynes promoted by Oxone®. The use of mild reaction conditions, efficiency and generality are characteristics of this new approach, which was suitable to convert different diselenides and 2-functionalized chalcogenoalkynes into a total of twenty-two 2,3-bis-organochalcogenyl-benzo[b]chalcogenophenes, eighteen of which were synthesized for the first time. The new compound 2-(butylselanyl)-3-(phenylselanyl)benzofuran was used as a substrate in the Pd-catalyzed reaction with phenylacetylene to access the Sonogashira's coupling derivative in good yield.

The selenophene derivatives are an important class of selenium-based heterocyclics. These compounds play an important role in prospecting new drugs, as well as in the development of new light-emitting materials. During the last years, several methods have been emerging to access the selenophene scaffold, employing a diversity of cyclization-based synthetic strategies, involving specific reaction partners and particularities. This review presents a comprehensive discussion on the recent advances in the synthesis of selenophene-based compounds, starting from different precursors, highlighting the main differences, the advantages, and limitations among them.

We describe herein an alternative transition-metal-free procedure to access 3,4-bis(butylselanyl)selenophenes and the so far unprecedented 3-(butylselanyl)-4-alkoxyselenophenes. The protocol involves the 5-endo-dig electrophilic cyclization of 1,3-diynes promoted by electrophilic organoselenium species, generated in situ through the oxidative cleavage of the Se-Se bond of dibutyl diselenide using Oxone^® as a green oxidant. The selective formation of the title products was achieved by controlling the solvent identity and the amount of dibutyl diselenide. By using 4.0 equiv of dibutyl diselenide and acetonitrile as solvent at 80 °C, four examples of 3,4-bis(butylselanyl)selenophenes were obtained in moderate to good yields (40–78%). When 3.0 equiv of dibutyl diselenide were used, in the presence of aliphatic alcohols as solvent/nucleophiles under reflux, 10 3-(butylselanyl)-4-alkoxyselenophenes were selectively obtained in low to good yields (15–80%).