A method for the intermolecular annulation of benzynes with allenes is disclosed.

A facile strategy to synthesize highly substituted dibenzoselenophenes and dibenzothiophenes by a domino hexadehydro-Diels–Alder reaction is reported in this article. The formation of three new C–C bonds, one new Caryl–Se/Caryl–S bond, and C–H σ-bond migration via one-pot multiterminal cycloaddition reactions were involved in over three transformations. The target tetracyclic compounds were prepared from tetraynes with a triphenylphosphine selenide or triphenylphosphine sulfide. This reaction played a pivotal role in constructing natural thio[seleno]phene cores, which were highly substituted, and is a robust method for producing fused heterocycles.