Cyclization of homopropargyl chalcogenides by copper(II) salts: selective synthesis of 2,3-dihydroselenophenes, 3-arylselenophenes, and 3-haloselenophenes/thiophenes.

Copper(II) halide mediated cyclization of homopropargyl chalcogenides gave three types of chalcogenophene derivatives. Selective product formation was achieved by controlling solvent, temperature, and atmosphere. By using CuBr2 and 1,2-dichloroethane at room temperature under ambient atmosphere, 4-bromo dihydroselenophene derivatives were obtained, whereas CuBr2 and 1,2-dichloroethane at reflux gave selectively 2-substituted selenophenes. When 1,2-dichloroethane was replaced by dimethylacetamide, 3-halo-selenophenes were obtained exclusively. The versatility of chalcogenophenes was also studied by reaction of 3-haloselenophenes with terminal alkynes under Sonogashira conditions affording the cross-coupled products. In addition, the reaction of 3-haloselenophenes with boronic acids gave the corresponding Suzuki-type products in good yields.